UA113513C2 - N- (3-carbamoylphenyl) -1H-pyrazole-5-carboxamide derivatives and their applications for the control of pest animals - Google Patents

Abstract

The invention relates to compounds of general formula (I), (I) in which the radicals AAA, A, L, Q, R, T and W have the meanings given in the description and the use of compounds for the control of pests. The invention also relates to methods and intermediates for the preparation of compounds of formula (I).

Description

in 2 points X / 1 - EE

Her Mr

F and xx A

And U and

M i vk o () in which radicals A; AND"; Az, Al, I, FO), EB", T and MM have the meaning given in the description and the use of the compounds for the control of pest animals. In addition, the invention relates to methods and intermediate compounds for obtaining compounds of the formula (1). and 2 schi X / 1 vk t m

F and xx A

And U y

M in that

This application relates to new halogen-substituted compounds, methods of their preparation and their use for the control of animal pests, in particular, arthropods, and especially insects, arachnids and nematodes.

It is known that certain halogen-substituted compounds have a herbicidal effect (cf. U. Ogd. Spet. 1997, 62(17), 5908-5919, U. Neiegosusi. Spet. 1998, 35(6), 1493-1499, MO 2004 /035545, MO 2004/106324, 005 2006/069132, MO 2008/029084).

In addition, it is known that certain halogen-substituted compounds are insecticidally active (EP1I911751).

In addition, certain halogen-substituted compounds are known to have cytokine-inhibitory activity (MO 00/07980).

Modern compositions for the protection of agricultural crops must meet many requirements, for example, regarding the effectiveness, stability and spectrum of their action and possible application. In this case, the issue of toxicity, compatibility with other active compounds or auxiliary substances of the formulations, as well as the cost of the synthesis of the active compound, play a role. In addition, persistence may occur. For all these reasons, the search for new crop protection agents can never be considered complete, and there is a constant need for new compounds having properties that, compared to known compounds, are improved at least in certain respects.

The purpose of this invention was to provide compounds that extend the spectrum of pesticides in various aspects and/or improve their activity.

It was unexpectedly discovered that the defined halogen-substituted compounds and their M-oxides and salts have biological properties and are particularly suitable for controlling animal pests, and, accordingly, can be used particularly well in the field of agrochemistry and in the field of veterinary medicine.

Similar compounds are already known from LO 2010/051926.

Halogen-substituted compounds according to the invention are defined by the general formula (1) 7 in Y id;

M. Her t M z ra i MITA,

WITH

M

' about (I) in which

Zo B' means hydrogen, optionally substituted C1-C8-alkyl, Co-C8-alkenyl, Co-C8-alkynyl, C3-C7-cycloalkyl, C1-C8-alkylcarbonyl, C1-C8-alkylcarbonyl, cyano-C1- C1-alkyl, aryl-(C1-C3)-alkyl, heteroaryl-(C:1-C3)-alkyl, chemical group

AND; stands for SEZ: or nitrogen,

Ag means SEZ or nitrogen,

Az means CE" or nitrogen

Ah; means CE: or nitrogen, but where nitrogen simultaneously means no more than three chemical groups A: - Ah; 82, VAZ, V? Her VK? independently of each other mean hydrogen, halogen, CM, MO", optionally substituted Ci-Cv-alkyl, Ci-Cv-halogenoalkyl, C3-C3e-cycloalkyl, / C3-Cv- halocycloalkyl, Ci-Cv-alkoxy, Si -Cv-halogenalkoxy, C:-Cv-alkylthio, C-Cv-haloalkylthio,

C.-Cv-alkylsulfinyl, C-Cv-halogenalkylsulfinyl, C-Cv-alkylsulfonyl, C1-Cv- haloalkylsulfonyl, C.i-Cv-alkylamino, M,M-di-Ci-Svalkylamino, M-C--Cv- alkylaminocarbonyl,

M-C3-C6-cycloalkylaminocarbonyl or (C1-C3-Alkoxy)carbonyl; if none of the groups Ag and Az does not represent nitrogen, KZ and K" together with the carbon atom to which they are attached can form a 5- or 6b-membered ring containing 0, 1 or 2 nitrogen atoms and/or 0 or 1 an oxygen atom and/or 0 or 1 sulfur atom, or if none of the groups A: and Ag is nitrogen, K:2 and EZ together with the carbon atom to which they are attached may form a b-membered ring containing 0, 1 or 2 nitrogen atoms;

M stands for oxygen or sulfur;

IN? means hydrogen, optionally substituted C1-C6-alkyl, aryl-(C1-C3)-alkyl, heteroaryl-(C1-

C3)-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3-C8-cycloalkyl, (C1-C3-alkyl)-C3-C8-cycloalkyl and (C3-C8-cycloalkyl)-C1-C3-alkyl , Ci-Cv-alkylcarbonyl, Ci-Cv-alkylcarbonyl; o means

I am

E means a bond, -СНе-, 5, 50, 505, -5-0Не-, -50-СН2-, -502-СНе-, -СНе-5-СНе-, -Сно-5О0О-СНе-, -Сно-502-СНе-, -5-СН2-СНе-, -BO-СНо-СНе-, -5О2-СНе-СНе-, -МАЕ-СнНе-, -СН»-МАУ-СнНе-;

B' means cyano or C(-5)MH"; 2" means optionally substituted C1-C6-haloalkyl or C3-C8-cycloalkyl, C3-C8- halocycloalkyl, and 72 means halogen, cyano, nitro or optionally substituted C1-C8-haloalkyl, C1-C8- alkylthio, C:-Cv-haloalkylthio, Ci-Cv-alkylsulfinyl, Ci-Cv-haloalkylsulfinyl, /C1-Cv- alkylsulfonyl, Ci-Cv-haloalkylsulfonyl, and 73 means hydrogen or optionally substituted C1-Cv-alkyl, Si -C4-alkenyl, C-C4-alkynyl,

C:i-Cv-haloalkyl;

Preference is given to compounds of formula (I) 7: uk id;

M in' 7 M7 with ra

OA A,

Ah Mu

With

Sh (I) in which

B' means hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxymethyl, ethoxymethyl, propoxymethyl, methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, sec-butylcarbonyl, tert -butylcarbonyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, cyanomethyl, 2-cyanoethyl, benzyl, 4-methoxybenzyl, pyrid-2-ylmethyl, pyrid-3-ylmethyl, pyrid-4-ylmethyl , 4-chloropyrid-3-ylmethyl; chemical group

AND; means CE: or nitrogen,

Ag means SEZ or nitrogen,

Az means CE" or nitrogen

Ag means CE: or nitrogen, but where nitrogen simultaneously means no more than three chemical groups A: - Ah;

IN? and 2?" independently of each other represent hydrogen, methyl, fluorine or chlorine and

BZ and B" independently of each other mean hydrogen, fluorine, chlorine, bromine, CM, MO", methyl, ethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, methoxy, ethoxy, n-propoxy, 1- methylethoxy, fluoromethoxy, difluoromethoxy, chlorodifluoromethoxy, dichlorofluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2,2-difluoroethoxy, pentafluoroethoxy, methyl sulfonyl, methylsulfinyl, trifluoromethylsulfonyl, trifluoromethylsulfinyl;

M stands for oxygen,

B5 means hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxymethyl, ethoxymethyl, propoxymethyl, methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, sec-butylcarbonyl, tert- butylcarbonyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, cyanomethyl, 2-cyanoethyl, benzyl, 4-methoxybenzyl, pyrid-2-ylmethyl, pyrid-3-ylmethyl, pyrid-4-ylmethyl, 4-chloropyrid-3-ylmethyl; o means

I am

E means bond or -СНе-;

B' means cyano or C(-5)MH"; 2! means difluoromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, bromodichloromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 1-fluoro-1-methylethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,2 ,2,2-t-tetrafluoroethyl, /1-chloro-1,2,2,2- tetrafluoroethyl, 2,2,2-trichloroethyl, 2-chloro-2,2-difluoroethyl, 1,1-difluoroethyl, pentafluoroethyl, pentafluoro-tert-butyl, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n-butyl, cyclopropyl, 1-chlorocyclopropyl, 1-fluorocyclopropyl, 1-bromocyclopropyl, 1-cyanocyclopropyl, 1-trifluoromethylcyclopropyl, cyclobutyl or 2,2-difluoro- 1-methylcyclopropyl, and 727 means halogen, cyano, nitro, difluoromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, bromodichloromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 1-fluoro-1-methylethyl, 2-fluoroethyl, 2,2-difluoroethyl , 2,2,2-trifluoroethyl, 1,2,2,2-tetrafluoroethyl, 1-chloro-1,2,2,2--tetrafluoroethyl, 2,2,2-trichloroethyl, 2-chloro-2,2- difluoroethyl, 1,1-difluoroethyl, pentafluoroethyl, pentafluoro-tert-butyl, heptafluoro-n-propyl, heptafluoroisopropyl, nona fluoro-n-butyl, methylthio, methylsulfinyl, methylsulfonyl, ethylthio, ethylsulfinyl, ethylsulfonyl, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, and 73 means hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert - butyl, ethenyl, 1-propenyl, 2-propenyl, ethynyl, 1-propynyl, 1-butynyl, difluoromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, chloromethyl, bromomethyl, 1-

Zo fluoroethyl, 1-fluoro-1-methylethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl;

Further particularly preferred compounds are compounds of the general formula (I) in which 7 is trifluoromethyl, 1-chlorocyclopropyl, 1-fluorocyclopropyl or pentafluoroethyl, 77 is trifluoromethyl, nitro, methylthio, methylsulfinyl, methylsulfonyl, fluorine, chlorine, bromine or iodine, 73 is methyl, ethyl, n-propyl or hydrogen,

AB' means hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxymethyl, ethoxymethyl, propoxymethyl, methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, sec-butylcarbonyl, tert -butylcarbonyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, cyanomethyl, 2-cyanoethyl, benzyl, 4-methoxybenzyl, pyrid-2-ylmethyl, pyrid-3-ylmethyl, pyrid-4-ylmethyl , 4-chloropyrid-3-ylmethyl,

A", Ag and A? mean CH,

Az means SE" and

B" means fluorine, chlorine, bromine or iodine,

B means hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,

Mu means oxygen and o means 1-cyanocyclopropyl.

Preference, in particular, is given to additional compounds in which 7! means trifluoromethyl, 1-chlorocyclopropyl, 1-fluorocyclopropyl or pentafluoroethyl, 72 means trifluoromethyl, chlorine or 73 means methyl,

B' means hydrogen, methyl, ethyl,

A", Ag and A? mean CH,

Az means SE and

B" means chlorine,

B stands for hydrogen, methyl, ethyl,

M stands for oxygen and o stands for 1-cyanocyclopropyl.

In addition, the invention includes new compounds of the general formulas (IMa), (IM), (ma), (MB) as better starting substances for the synthesis of compounds of the general formula (I).

Compounds of the general formulas (IMa) and (MB) are the best variants of the precursors of the general formula (IM), for example, according to reaction schemes 1, 2 and 3. Preparation of compounds of the general formula (I), among other things, is preferably carried out using these compounds. Compounds of the general formula (IM) are usually converted by reduction into compounds (IMa).

The compounds (IMa) and (MB) are defined by the general formulas below

MO, MN, v- v" M v- v" M n y n y v' y v' y yo (Mb) yo (ma) in which

B2, VAZ, B? Her K? independently of each other mean hydrogen, halogen, cyano, nitro, optionally substituted Ci-Cv-alkyl, Ci-Cv-halogenoalkyl, C3-C3e-cycloalkyl, / C3-Cv- halocycloalkyl, Ci-Cv-alkoxy, Ci- C:-Cv-haloalkylthio, C:-Cv-haloalkylthio,

C.-Cv-alkylsulfinyl, C-Cv-haloalkylsulfinyl, C-Cv-alkylsulfonyl, C1-Cv- haloalkylsulfonyl, C-i-Cv-alkylamino, M,M-di-C1-Cv-alkylamino, M-C1-Cv -alkylaminocarbonyl,

M-C3-C6-cycloalkylaminocarbonyl or (C1-C3-Alkoxy)carbonyl.

Preference is given to compounds of the general formulas (IMa), (MB), in which

B2 and E5 mean hydrogen or halogen, and

B3 and B" mean hydrogen, halogen, cyano, nitro, Ci-Cv-alkyl, Ci-Cv-haloalkyl, C3-Cv-cycloalkyl, C3-Cv-halocycloalkyl, Ci-Cv-alkylthio, Ci--Cv-haloalkylthio, Ci-Cv-alkylsulfinyl,

C1-Cv-halogenalkylsulfinyl, C-Cv-alkylsulfonyl, C-Cv-haloalkylsulfonyl.

Particular preference is given to compounds of the general formulas (IMa), (IM), in which

B2 means hydrogen or fluorine, and

BZ stands for hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl, cyclopropyl, 1-chlorocyclopropyl, 1-fluorocyclopropyl, methylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl,

With trifluoromethylsulfonyl, and

B" means hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl, cyclopropyl, 1-chlorocyclopropyl, 1-fluorocyclopropyl , methylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl, and

IN? means hydrogen.

Even more preference is given to compounds of the general formulas (IMa), (IMB), in which 82 and 25 are hydrogen, and

WZ means hydrogen, fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl, methylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl, and

IN? means fluorine, chlorine, bromine, iodine, methyl, and

B" means hydrogen.

Compounds of the general formulas (Ma) and (MB) are the best variants of the precursors of the general formula (M), for example, according to reaction schemes 1, 2 and 8. Preparation of compounds of the general formula (I), among other things, is preferably carried out using these compounds.

Compounds (Ma) and (M) are determined by the general formulas below x 7 x ud

IOM / o-u IOM ron

And I gom tm in which

BO X' means halogen, cyano and C-C4-haloalkyl, and

72 means halogen, cyano, nitro or optionally substituted C1-Cv-haloalkyl, C1-Cv-alkylthio, C:-Cv-haloalkylthio, C1-Cv-alkylsulfinyl, C1-Cv-haloalkylsulfinyl, /C1-Cv- alkylsulfonyl, C1-C6-haloalkylsulfonyl, and 73 is hydrogen or optionally substituted C1-C6-alkyl, C1-C4-alkenyl, C1-C4-alkynyl, C1-C6-haloalkyl, and

U means optionally substituted C:-Cv-alkyl.

Preference is given to compounds of the general formulas (Ma) and (MB), in which

X' means fluorine, chlorine, bromine, cyano, and C1-C0-haloalkyl, and 22 means halogen, cyano, nitro, difluoromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, bromodichloromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 1-fluoro- 1-methylethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,2,2,2-tetrafluoroethyl, 1-chloro-1,2,2,2-tetrafluoroethyl, 2,2 ,2-trichloroethyl, 2-chloro-2,2-difluoroethyl, 1,1-difluoroethyl, pentafluoroethyl, pentafluoro-tert-butyl, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n-butyl, methylthio, methylsulfinyl, methylsulfonyl, ethylthio , ethylsulfinyl, ethylsulfonyl, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, and 73 means hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, ethenyl, 1-propenyl, 2-propenyl, ethynyl, 1-propynyl, 1-butynyl, difluoromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 1-fluoro-1-methylethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2, 2-trifluoroethyl, i

U means optionally substituted C:-Cv-alkyl.

Particular preference is given to compounds of the general formulas (ma) and (MB), in which

X' is fluoro, chloro, trifluoromethyl, or pentafluoroethyl, and 72 is trifluoromethyl, nitro, methylthio, methylsulfinyl, methylsulfonyl, fluoro, chloro, bromo, or iodo, and 73 is methyl, ethyl, n-propyl, or hydrogen, and

Y represents methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl.

According to the invention, "alkyl" - by itself or as part of a chemical group - means hydrocarbons with a normal or branched chain, preferably containing from 1 to 6 carbon atoms, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,

Co) tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylpropyl, 1,3-dimethylbutyl, 1,4-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3- dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl and 2-ethylbutyl. In addition, preference is given to alkyl groups containing from 1 to 4 carbon atoms, such as, among others, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. Alkyl groups according to the invention can be substituted by one or more identical or different radicals.

According to the invention, "alkenyl" - by itself or as part of a chemical group - means hydrocarbons with a normal or branched chain, preferably containing from 2 to 6 carbon atoms and at least one double bond, such as, for example, vinyl, 2 -propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl -2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2 -dimethyl-2-propenyl, 1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl -2-pentenyl, 4-methyl-2-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4 -pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl , 1,3-dimethyl-2-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 1-ethyl-2-butenyl, 1 - ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-33-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl and 1-ethyl- 2-methyl-2-propenyl. Alkenyl groups containing from 2 to 4 carbon atoms are also preferred, such as, among others, 2-propenyl, 2-butenyl or 1-methyl-2-propenyl.

Alkenyl groups according to the invention can be substituted by one or more identical or different radicals.

According to the invention, "alkynyl" - by itself or as part of a chemical group - means hydrocarbons with a normal or branched chain preferably containing from 2 to 6 carbon atoms and at least one triple bond, such as, for example, 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2- butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3- pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-60 methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-3 -butynyl, 1,2-dimethyl-

3-butynyl, 2,2-dimethyl-3-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl and 2,5-hexadienyl. In addition, preference is given to alkynyl groups containing from 2 to 4 carbon atoms, such as, among others, ethynyl, 2-propynyl or 2-butynyl-2-propenyl. Alkynyl groups according to the invention can be substituted by one or more identical or different radicals.

According to the invention, "cycloalkyl" - by itself or as part of a chemical group - means mono-, bi- or tricyclic hydrocarbons preferably containing from 3 to 10 carbons, such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl , cyclooctyl, bicyclo(2.2.1|)heptyl, bicyclo(2.2.2ococtyl or adamantyl. Cycloalkyl groups containing 3, 4, 5, b or 7 carbon atoms are also preferred, such as, inter alia, cyclopropyl or cyclobutyl Cycloalkyl groups according to the invention can be substituted by one or more identical or different radicals.

According to the invention, "alkylcycloalkyl" means mono-, bi- or tricyclic alkylcycloalkyl, preferably containing from 4 to 10 or from 4 to 7 carbon atoms, such as, for example, ethylcyclopropyl, isopropylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl.

In addition, preference is given to alkylcycloalkyl groups containing 4, 5 or 7 carbon atoms, such as, among others, ethylcyclopropyl or 4-methylcyclohexyl. Alkylcycloalkyl groups according to the invention can be substituted by one or more identical or different radicals.

According to the invention, "cycloalkylalkyl" means mono-, bi- or tricyclic cycloalkylalkyl, preferably containing from 4 to 10 or from 4 to 7 carbon atoms, such as, for example, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl and cyclopentylethyl. Preference is also given to cycloalkylalkyl groups containing 4, 5 or 7 carbon atoms, such as, inter alia, cyclopropylmethyl or cyclobutylmethyl.

Cycloalkylalkyl groups according to the invention can be substituted by one or more identical or different radicals.

According to the invention, "halogen" means fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine.

Halogen-substituted chemical groups according to the invention, such as, for example, haloalkyl, halocycloalkyl, haloalkyloxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl are mono- or polysubstituted by halogen up to the maximum possible number of substituents. In the case of polysubstitution with a halogen, the halogen atoms may be the same or different, and may all be attached to one or more carbon atoms. Here, halogen means in particular fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine and especially preferably fluorine.

According to the invention, "halocycloalkyl" means a mono-, bi- or tricyclic halocycloalkyl containing preferably from 3 to 10 carbon atoms, such as, among others, 1-fluorocyclopropyl, 2-fluorocyclopropyl or 1-fluorocyclobutyl. Halogencycloalkyl containing 3, 5 or 7 carbon atoms is also preferred. Halogencycloalkyl groups according to the invention can be substituted by one or more identical or different radicals.

According to the invention, "haloalkyl" "haloalkenyl" or "haloalkynyl" means halogen-substituted alkyl, alkenyl or alkynyl groups containing preferably from 1 to 9 identical or different halogen atoms, such as, for example, monohaloalkyl, such as CH2CNeCl,

СНеСНеЕ, СНОИИСН», СНЕСН», СНоСИ, СНЕ; perhaloalkyl, such as C33 or C33 or C3C3:; polyhaloalkyl, such as СНЕ», СНР, СН»СНЕСИ, СНО», СЕР25СЕ2Н, СНеСЕ». This, accordingly, is also applicable to haloalkenyl and other halogen-substituted radicals. Halogenalkoxy means, for example, OSEz, OSNE", OSNoE, OSER»2SEz, OSNoCE: and OSN»SNEeSi.

Additional examples of haloalkyl groups are trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 2-chloro-2 ,2-difluoroethyl, pentafluoroethyl and pentafluoro-tert-butyl. Preference is given to haloalkyl groups containing from 1 to 4 carbon atoms and from 1 to 9, preferably from 1 to 5, the same or different halogen atoms selected from the group consisting of fluorine, chlorine and bromine. Particular preference is given to haloalkyl groups containing 1 or 2 carbon atoms and from 1 to 5 identical or different halogen atoms selected from the group consisting of fluorine and chlorine, such as, inter alia, difluoromethyl, trifluoromethyl or 2,2-difluoroethyl .

According to the invention, "hydroxyalkyl" means an alcohol with a normal or branched chain, preferably containing from 1 to b carbon atoms, such as, for example, methanol, 60 ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol. preference,

in addition, hydroxyalkyl groups containing from 1 to 4 carbon atoms are given.

Hydroxyalkyl groups according to the invention can be substituted by one or more identical or different radicals.

According to the invention, "Alkoxy" means O-alkyl with a normal or branched chain, preferably containing from 1 to 6 carbon atoms, such as, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec- butoxy and tert-butoxy. In addition, preference is given to alkoxy groups containing from 1 to 4 carbon atoms. Alkoxy groups according to the invention can be substituted by one or more identical or different radicals.

According to the invention, "haloalkyl" means halogen-substituted O-alkyl with a normal or branched chain, preferably containing from 1 to 6 carbon atoms, such as, among others, difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 1,1, 2,2-tetrafluoroethoxy, 2,2,2-trifluoroethoxy and 2-chloro-1,1,2-trifluoroethoxy. In addition, preference is given to haloalkoxy groups containing from 1 to 4 carbon atoms. Halogenalkoxy groups according to the invention can be substituted by one or more identical or different radicals.

According to the invention, "alkylthio" means C-alkyl with a normal or branched chain, preferably containing from 1 to b carbon atoms, such as, for example, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec- butylthio and tert-butylthio. In addition, preference is given to alkylthio groups containing from 1 to 4 carbon atoms. Alkylthio groups according to the invention can be substituted by one or more identical or different radicals.

Examples of haloalkylthioalkyl groups, i.e. halogen-substituted alkylthio groups, are, among others, difluoromethylthio, trifluoromethylthio, trichloromethylthio, chlorodifluoromethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 1,1,2,2-tetrafluoroethylthio, 2, 2,2-trifluoroethylthio or 2-chloro-1,1,2-trifluoroethylthio.

According to the invention, "alkylsulfinyl" means a normal or branched chain alkylsulfinyl preferably containing from 1 to 6 carbon atoms, such as, for example, methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl and tert-butylsulfinyl. In addition, preference is given

From alkylsulfinyl groups containing from 1 to 4 carbon atoms. Alkylsulfinyl groups according to the invention can be substituted by one or more identical or different radicals.

Examples of haloalkylsulfinyl groups, i.e. halogen-substituted alkylsulfinyl groups, are, among others, difluoromethylsulfinyl, trifluoromethylsulfinyl, trichloromethylsulfinyl, chlorodifluoromethylsulfinyl, 1-fluoroethylsulfinyl, 2-fluoroethylsulfinyl, 2,2-difluoroethylsulfinyl, 1,1,2,2-tetrafluoroethylsulfinyl, 2, 2,2-trifluoroethylsulfinyl and 2-chloro-1,1,2-trifluoroethylsulfinyl.

According to the invention, "alkylsulfonyl" means a normal or branched chain alkylsulfonyl preferably containing from 1 to 6 carbon atoms, such as, for example, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, t-butylsulfonyl and tert-butylsulfonyl. In addition, preference is given to alkylsulfonyl groups containing from 1 to 4 carbon atoms. Alkylsulfonyl groups according to the invention can be substituted by one or more identical or different radicals.

Examples of haloalkylsulfonyl groups, i.e. halogen-substituted alkylsulfonyl groups, are, among others, difluoromethylsulfonyl, trifluoromethylsulfonyl, trichloromethylsulfonyl, chlorodifluoromethylsulfonyl, 1-fluoroethylsulfonyl, 2-fluoroethylsulfonyl, 2,2-difluoroethylsulfonyl, 1,1,2,2-tetrafluoroethylsulfonyl, -2 ,2,2-trifluoroethylsulfonyl and 2-chloro-1,1,2-trifluoroethylsulfonyl.

According to the invention, "alkylcarbonyl" means alkyl-C(-O) with a normal or branched chain, preferably containing from 2 to 7 carbon atoms, such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, sec-butylcarbonyl and tert-butylcarbonyl . In addition, preference is given to alkylcarbonyl groups containing from 1 to 4 carbon atoms. Alkylcarbonyl groups according to the invention can be substituted by one or more identical or different radicals.

According to the invention, "cycloalkylcarbonyl" means cycloalkylcarbonyl with a normal or branched chain, preferably containing from 3 to 10 carbon atoms in the cycloalkyl fragment, such as, for example, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cycloheptylcarbonyl, cyclooctylcarbonyl, 60 bicyclo|2.2. 1|)heptyl, bicyclo|(2.2.2)octylcarbonyl and adamantylcarbonyl. Preference is also given to cycloalkylcarbonyl containing 3, 5 or 7 carbon atoms in the cycloalkyl fragment. Cycloalkylcarbonyl groups according to the invention can be substituted by one or more identical or different radicals.

According to the invention, "Alkoxycarbonyl" - alone or as a constituent part of a chemical group - means a normal or branched chain alkoxycarbonyl, preferably containing from 1 to 6 carbon atoms, or containing from 1 to 4 carbon atoms in an alkoxy moiety, such as, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, t-butoxycarbonyl and tert-butoxycarbonyl. Alkoxycarbonyl groups according to the invention can be substituted by one or more identical or different radicals.

According to the invention, "alkylaminocarbonyl" means a normal or branched chain alkylaminocarbonyl containing preferably from 1 to 6 carbon atoms or from 1 to 4 carbon atoms in the alkyl moiety, such as, for example, methylaminocarbonyl, ethylaminocarbonyl, n-propylaminocarbonyl, isopropylaminocarbonyl, sec-butylaminocarbonyl and tert-butylaminocarbonyl. Alkylaminocarbonyl groups according to the invention can be substituted by one or more identical or different radicals.

According to the invention, "M,M-dialkylaminocarbonyl" means M,M-dialkylaminocarbonyl with a normal or branched chain containing preferably from 1 to 6 carbon atoms or from 1 to 4 carbon atoms in an alkyl moiety, such as, for example, M, M-dimethylaminocarbonyl, M,M-diethylaminocarbonyl, M,M-di(n-propylamino)carbonyl, M,M-di(isopropylamino)carbonyl and M,M-di-(5-butylamino)carbonyl. M,M-dialkylaminocarbonyl groups according to the invention can be substituted by one or more identical or different radicals.

According to the invention, "aryl" means a mono-, bi- or polycyclic aromatic system containing preferably from 6 to 14, in particular from 6 to 10 carbon atoms in the ring, such as, for example, phenyl, naphthyl, anthryl, phenanthrenyl, preferably phenyl. In addition, aryl also means polycyclic systems such as tetrahydronaphthyl, indenyl, indanyl, fluorenyl, biphenylyl, where the site of attachment is on the aromatic system. Aryl groups according to the invention can be substituted by one or more identical or different radicals.

Examples of substituted aryls are arylalkyl groups, which may also be substituted by one

Zo or several identical or different radicals in the alkyl and/or aryl fragment.

Examples of such arylalkyl groups are, among others, benzyl and 1-phenylethyl.

According to the invention, "heterocycle", "heterocyclic ring" or "heterocyclic ring system" means a carbocyclic ring system that contains at least one ring in which at least one carbon atom is replaced by a heteroatom, preferably a heteroatom from the group consisting of M, O, 5, P, B, 5i, 5e, and which is saturated, unsaturated or heteroaromatic and may be unsubstituted or substituted by a substituent 7, where the point of attachment is located on a ring atom. Unless otherwise specified, the heterocyclic ring contains preferably from 3 to 9 atoms in the ring, especially from 3 to 6 atoms in the ring, and one or more, preferably from 1 to 4, in particular 1, 2 or 3, heteroatoms in the heterocyclic ring, preferably from the group consisting of M, O and 5, but two oxygen atoms cannot be located directly next to each other. Heterocyclic rings usually contain no more than 4 nitrogen atoms and/or no more than 2 oxygen atoms and/or no more than 2 sulfur atoms. If the heterocyclyl radical or heterocyclic ring is optionally substituted, it may be condensed with other carbocyclic or heterocyclic rings. In the case of an optionally substituted heterocyclyl, the invention also covers polycyclic systems such as, for example, 8-azabicyclo/3.2.1|octanyl or 1-azabicyclo|2.2.1)heptyl. In the case of optionally substituted heterocyclyl, the invention also covers spirocyclic systems such as, for example, 1-oxa-5-azaspiro(2.3Z|hexyl.

Heterocyclic groups according to the invention are, for example, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, dihydropyranyl, tetrahydropyranyl, dioxanyl, pyrrolinyl, pyrrolidinyl, imidazolinyl, imidazolidinyl, thiazolidinyl, oxazolidinyl, dioxolanyl, dioxolyl, pyrazolidinyl, tetrahydrofuranyl, dihydrofuranyl, oxtanyl azetidinyl, aziridinyl, oxazetidinyl, oxaziridinyl, oxazepanil, oxazinanil, azepanil, oxopyrrolidinyl, dioxopyrrolidinyl, oxomorpholinyl, oxopiperazinil, and oxepanil.

Heteroarylenes, i.e. heteroaromatic systems, are of particular importance. According to the invention, the term heteroaryl means heteroaromatic compounds, that is, fully unsaturated aromatic heterocyclic compounds that fall under the above definition of heterocycles.

Preference is given to 5-7-membered rings containing from 1 to 3, preferably 1 or 2, the same or different heteroatoms from the above group. Heteroaryl groups according to the invention are, for example, furyl, thienyl, pyrazolyl, imidazolyl, 1,2,3- and 1,2,4-triazolyl, 60 isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-, 1,3 ,4-, 1,2,4- and 1,2,5-oxadiazolyl, azepinyl, pyrrolyl,

pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-, 1,2,4- and 1,2,3-triazinyl, 1,2,4-, 1,5,2-, 1,3,6- and 1,2,6-oxazinyl, oxepinyl, thiepinyl, 1,2,4-triazolonyl, and 1,2,4-diazepinyl. Heteroaryl groups according to the invention can also be substituted by one or more identical or different radicals.

Substituted groups such as substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, phenyl, benzyl, heterocyclyl and heteroaryl radicals are, for example, substituted radicals derived from an unsubstituted base structure, where the substituents are, for example, one or more, preferably 1, 2 or 3, radicals from the group consisting of halogen, alkoxy, alkylthio, hydroxyl, amino, nitro, carboxyl or a group equivalent to a carboxyl group, cyano, isocyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and M,M -dialkylaminocarbonyl, substituted amino such as acylamino, mono- and M,M-dialkylamino, trialkylsilyl and optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted heterocyclyl, wherein each of the latter cyclic groups may also be attached via heteroatoms or divalent functional groups, such as the aforementioned alkyl radicals, and alkylsulfinyl, including both enantiomers of the alkylsulfonyl group, alkylsulfonyl, alkylphosphinyl, alc ylphosphonyl and, in the case of cyclic radicals (- "cyclic skeleton"), also alkyl, haloalkyl, alkylthioalkyl, alkoxyalkyl, optionally substituted mono- and M,M-dialkylaminoalkyl and hydroxyalkyl.

The term "substituted groups", such as substituted alkyl, etc., includes as substituents, in addition to the saturated hydrocarbon radicals mentioned, corresponding unsaturated aliphatic and aromatic radicals, such as optionally substituted alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio , alkynylthio, alkenyloxycarbonyl, alkynyloxycarbonyl, alkenylcarbonyl, alkynylcarbonyl, mono- and

M,M-dialkenylaminocarbonyl, mono- and dialkynylaminocarbonyl, mono- and M,M-dialkenylamino, mono- and

M,M-dialkynylamino, trialkenylsilyl, trialkynylsilyl, optionally substituted cycloalkenyl, optionally substituted cycloalkynyl, phenyl, phenoxy, etc. In the case of substituted cyclic radicals with aliphatic components in the ring, also included are cyclic systems with these substituents attached to the ring via a double bond, for example systems containing an alkylidene group such as methylidene or ethylidene, or an oxo group, an imino group, or a substituted imino group .

Ko) When two or more radicals form one or more rings, they can be carbocyclic, heterocyclic, saturated, partially saturated, unsaturated, for example, also aromatic and additionally substituted.

The substituents mentioned by way of example ("first level of substituents"), if they contain hydrocarbon-containing moieties, may optionally be further substituted ("second level of substituents"), for example, by one of the substituents as defined for the first level of substituents.

Appropriate further levels of substitutes are possible. The term "substituted radical" preferably covers only one or two levels of substituents.

Preferred substituents for levels of substituents are, for example, amino, hydroxy, halogen, nitro, cyano, isocyano, mercapto, isothiocyanato, carboxyl, carboxamide, 5E5, aminosulfonyl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, M-monoalkylamino, M,M -dialkylamino, M-alkanoylamino, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryloxycarbonyl, alkanoyl, alkenylcarbonyl, alkynylcarbonyl, arylcarbonyl, alkylthio, cycloalkylthio, alkenylthio, decylsulfenylthio, alkynylthio, and both are included enantiomers of the alkylsulfinyl group, alkylsulfonyl, M-monoalkylaminosulfonyl, M,M-dialkylaminosulfonyl, alkylphosphinyl, alkylphosphonyl, where in the case of alkylphosphinyl and alkylphosphonyl both enantiomers are included, M-alkylaminocarbonyl,

M,M-dialkylaminocarbonyl, M-alkanoylaminocarbonyl, M-alkanoyl-M-alkylaminocarbonyl, aryl, aryloxy, benzyl, benzyloxy, benzylthio, arylthio, arylamino, benzylamino, heterocyclyl, and trialkylsilyl.

Замісники, які складаються із більшої кількості рівнів замісників, переважно означають алкоксіалкіл, алкілтіосалкіл, алкілтіоалкокси, алкоксіалкокси, фенетил, бензилокси, галогеналкіл, галогенциклоалкіл, галогеналкокси, галогеналкілтіо, галогеналкілсульфініл, галогеналкілсульфоніл, галогеналканоїл, галогеналкілкарбоніл, галогеналкоксикарбоніл, галогеналкоксіалкокси, галогеналкоксіалкілтіо, галогеналкоксіалканоїл, галогеналкоксіалкіл.

In the case of radicals containing carbon atoms, radicals containing 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, especially 1 or 2 carbon atoms are preferred. Preference is usually given to substituents from the group that includes halogen, for example, fluorine and chlorine, (C1-C4)-alkyl, preferably methyl or ethyl, (C1-C4)-haloalkyl, preferably 60 trifluoromethyl, (Ci-C4)-alkoxy, preferably methoxy or ethoxy, (C1-C4)-halogeno, nitro and cyano. Methyl, methoxy, fluorine and chlorine substituents are particularly preferred here.

Substituted amino, such as mono- or disubstituted amino, means a radical from the group consisting of a substituted amino that is M-substituted, for example, by one or two identical or different radicals from the group consisting of alkyl, hydroxy, amino, alkoxy, acyl and aryl; preferably M-mono- and M,M-dialkylamino, (for example, methylamino, ethylamino, M,M-dimethylamino,

M,M-diethylamino, M,M-di-n-propylamino, M,M-diisopropylamino or M,M-dibutylamino), M-mono- or M,M-dialkoxyalkylamino groups (e.g., M-methoxymethylamino, M-methoxyethylamino, M,M-di(methoxymethyl)amino or M,M-di(methoxyethyl)amino), M-mono- and M,M-diarylamino, such as optionally substituted anilines, acylamino, M,M-diacylamino, M- alkyl-M-arylamino, M-alkyl-M-acylamino, as well as saturated M-heterocycles; preference is given here to alkyl radicals containing from 1 to 4 carbon atoms; in this case, aryl preferably means phenyl or substituted phenyl; for acyl, the definition given below is used, preferably (C1-C4)-alkanoyl.

The same applies to substituted hydroxylamino or hydrazino.

According to the invention, the term "cyclic amino groups" covers heteroaromatic or aliphatic ring systems containing one or more nitrogen atoms. Heterocycles are saturated or unsaturated, consist of one or more optionally condensed ring systems and optionally contain additional heteroatoms, such as, for example, one or two nitrogen, oxygen and/or sulfur atoms. In addition, the term also includes groups containing a spiro ring or a bridged ring system. The number of atoms that form cyclic amino groups is not limited, in the case of a one-ring system, for example, the groups can consist of 3-8 atoms in the ring, and in the case of a two-ring system - from 7-11 atoms.

Examples that may be mentioned of cyclic amino groups that contain saturated and unsaturated monocyclic groups containing a nitrogen atom as a heteroatom are 1-azetidinyl, pyrrolidino, 2-pyrrolidin-1-yl, 1-pyrrolyl, piperidino, 1,4- dihydropyrazin-1-yl, 1,2,5,6-tetrahydropyrazin-1-yl, 1,4-dihydropyridin-1-yl, 1,2,5,6-tetrahydropyridin-1-yl, homopiperidinyl; examples that may be mentioned of cyclic amino groups containing saturated and unsaturated monocyclic groups containing two or more nitrogen atoms as heteroatoms are 1-imidazolidinyl, 1-imidazolyl, 1-pyrazolyl, 1-triazolyl, 1-tetrazolyl, 1-piperazinyl, 1-homopiperazinyl, 1,2-dihydropiperazin-1-yl, 1,2-dihydropyrimidin-1-yl, perhydropyrimidin-1-yl, 1,4-diazacycloheptan-1-yl; examples

Of the cyclic amino groups containing saturated and unsaturated monocyclic groups containing one or two oxygen atoms and from one to three nitrogen atoms as heteroatoms, there are, for example, oxazolidin-3-yl, 2,3-dihydroisoxazol-2-yl, isoxazole -g2-yl, 1,2,3-oxadiazin-2-yl, morpholino, examples that may be mentioned, of cyclic amino groups containing saturated and unsaturated monocyclic groups containing from one to three nitrogen atoms and from one to two sulfur atoms as heteroatoms are thiazolidin-3-yl, isothiazolin-2-yl, thiomorpholino, or dioxothiomorpholino; examples that may be mentioned of cyclic amino groups containing saturated and unsaturated fused cyclic groups are indol-yl, 1,2-dihydrobenzimidazol-1-yl, perhydropyrrolo|1,2-a|pyrazin-2-yl; examples that may be mentioned of cyclic amino groups containing spirocyclic groups are 2-azaspiro|4,5|decan-2-yl; examples that may be mentioned of cyclic amino groups containing bridging heterocyclic groups are 2-azabicyclo|2.2.1|)heptan-7-yl.

Substituted amino also includes quaternary ammonium compounds (salts) with four organic substituents on the nitrogen atom.

Optionally substituted phenyl is preferably a phenyl which is unsubstituted or mono- or polysubstituted, preferably substituted up to three times by the same or different radicals from the group consisting of halogen, (C1-Ca)-alkyl, (C1-Ca)- Alkoxy, (C1-Ca)-Alkoxy-(C1-Ca)-Alkoxy, (C1-Ca)-Alkoxy-(C1-Ca4)-Alkyl, (C1-C4)-Haloalkyl, (C1-C4)-Haloalkyl, (С1-Са)- alkylthio, (С1-С4)-haloalkylthio, cyano, isocyano and nitro, for example 0-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-fluorophenyl, 2-, 3- and 4-trifluoromethyl- and - trichloromethylphenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, 0-, m- and p-methoxyphenyl.

Optionally substituted cycloalkyl is preferably cycloalkyl which is unsubstituted or mono- or polysubstituted, preferably substituted up to three times by the same or different radicals from the group which includes halogen, cyano, (C1-C4)-alkyl, (C1-C4 )- Alkoxy, (C1-C4)-Alkoxy-(C1-Ca4)-Alkoxy, (C1-Ca)-Alkoxy-(C1-C4)-Alkyl, (C1-Ca4)-haloalkyl and (C1-

Са4)-halogenalkoxy, especially one or two (С1-Са)-alkyl radicals.

An optionally substituted heterocyclyl is preferably a heterocyclyl that is unsubstituted or mono- or polysubstituted, preferably substituted up to three times by the same or different radicals from the group consisting of halogen, cyano, (C1-C4)-alkyl, (C1-C4 )- Alkoxy, (C1-Ca)-Alkoxy-(C1-Ca)-Alkoxy, (C1-Ca)-Alkoxy-(C1-Ca4)-Alkyl, (C1-Ca)-haloalkyl, (Cch-

C4)-halogenalkoxy, nitro and oxo, especially mono- or polysubstituted by radicals from the group 60 which includes halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkyl and oxo, the most preferably substituted by one or two (C1-C4)-alkyl radicals.

Examples of alkyl-substituted heteroaryl groups are furylmethyl, thienylmethyl, pyrazolylmethyl, imidazolylmethyl, 1,2,3- and 1,2,4-triazolylmethyl, isoxazolylmethyl, thiazolylmethyl, isothiazolylmethyl, 1,2,3-, 1,3,4-, 1,2,4- and 1,2,5-oxadiazolylmethyl, azepinylmethyl, pyrrolylmethyl, pyridylmethyl, pyridazinylmethyl, pyrimidinylmethyl, pyrazinylmethyl, 1,3,5-, 1,2,4- and 1,2,3- triazinylmethyl, 1 .

Salts which are suitable according to the invention, compounds according to the invention, for example salts with bases or acid addition salts, are all conventional non-toxic salts, preferably salts acceptable from the point of view of agriculture and/or physiologically acceptable salts. For example, salts with bases or acid-addition salts. Salts with inorganic bases are preferred, such as, for example, alkali metal salts (eg sodium, potassium or cesium salts), alkaline earth metal salts (eg calcium or magnesium salts), ammonium salts or salts with organic bases, in particular with organic amines such as, for example, triethylammonium, dicyclohexylammonium, /M,M'-dibenzylethylenediammonium, pyridinium, picolinium or ethanolammonium salts, salts with inorganic acids (for example hydrochlorides, hydrobromides, dihydrosulfates, trihydrosulfates or phosphates), salts with organic carboxylic acids or organic sulfonic acids (for example, formates, acetates, trifluoroacetates, maleates, tartrates, methanesulfonates, benzenesulfonates or 4-toluenesulfonates). It is known that t-amines, such as some of the compounds according to the invention, are capable of forming M-oxides, which also mean salts according to the invention.

The compounds according to the invention can, depending on the nature of the substituents, be in the form of geometric and/or optically active isomers or appropriate mixtures of isomers in different compositions. These stereoisomers are, for example, enantiomers, diastereomers, atropisomers or geometric isomers. Accordingly, the invention includes pure stereoisomers and any mixture of these isomers.

If necessary, the compounds according to the invention can exist in different polymorphic forms or in the form of mixtures of different polymorphic forms. Both pure polymorphs and mixtures of polymorphs are provided by this invention and can be used in accordance with the invention.

The compounds of general formula (I) can be mixed or applied together with other insecticidal, nematicidal, acaricidal or antimicrobial active compounds. In these mixtures or combined applications, there is a synergistic effect, that is, the observed effect of these mixtures or combined applications exceeds the sum of the actions of individual active compounds in such applications. Examples of such components for mixtures or combinations are: (1) Acetylcholinesterase inhibitors (ACEIs), such as carbamates, such as alanicarb (11-1-1), aldicarb (11-1-2), bendiocarb (1I-1-3), benfuracarb (11-1-4), butocarboxim (1I-1-5), butoxycarboxim (1I1-1-6), carbaryl (11-1-7), carbofuran (1I-1-8), carbosulfan (1I-1- 993, etiofencarb (11-1-140), fenobucarb (11-1-11), formetanut (1I-1-12), furatiocarb (11-1-13), isoprocarb (11-1-14), methiocarb (11 -1-15), methomyl (1I-1-16), metolcarb (1I-1-17), oxamyl (1I1-1-18), pirimicarb (11-1-19), propoxur (1I-1-20) , thiodicarb (11-1-21), thiophanox (1I-1-22), triazamate (1I-1-23), trimetacarb (11-1-24), HMO (1I-1-25) and xylylcarb (11- 1-26); or organophosphates, for example acephate (11-1-27), azamethifos (1I-1-28), azinphos-ethyl (11-1-29), azinphos-methyl (1I1-1-30), cadusaphos (11-1-31), chlorethoxyphos (1I1-1-32), chlorfenvinphos (11-1-33), chlormephos (11-1-34), chlorpyrifos (1I-1-35), chlorpyrifos-methyl (1I- 1-36), coumaphos (II-1-37), cyanophos (II-1-38), where meton-5-methyl (1I-1-39), diazinon (1I-1-40), dichlorvos/uOMR (1I1-1-41), dicrotophos (11-1-42), dimethoate (11-1-43) , dimethylvinphos (1I-1-44), disulfoton (11-1-45), ERM (1I-1-46), ethion (I1I-1-47), ceprofos (1I-1-48), famfur (1I1- 1-49), fenamiphos (1I1-1-50), fenitrothion (11-1-51), fenthion (1I1-1-52), fostiazate (1I1-1-53), heptenophos (1I-1-54), Imiciaafos (11-1-55), isofenphos (II-1-56), isopropyl O-(methoxyaminothiophosphoryl) salicylate (1I-1-57), isoxathion (11-1-58), malathion (II-1-59) , mecarbam (11-1-60), methamidophos (11-1-61), methidathion (1I1-1-62), mevinphos (1I1-1-63), monocrotophos (11-1-64), naled (1I- 1-65), ometoate (1I1-1-66), oxydemeton-methyl (1I-1-67), parathion (11-1-68), parathion-methyl (1I-1-69), phentoate (1I1-1 -70), phorate (11-1-71), phosalon (11-1-72), phosmet (II-1-73), phosphamidon (1I-1-74), phoxim (11-1-75), primiphos -methyl (1I-1-76), profenofos (I-1-77), propetamphos (1I-1-78), prothiophos (11-1-79), pyraclophos (11-1-80), pyridafenthion (11- 1-81), quinalphos (1-1-82), sulfotep (11- 1-83), tebupirimphos (11-1-84), temephos (11-1-85), terbuphos (1I1-1-86), tetrachlorvinphos (1I1-1-87), thiometon (1I-1-88), triazophos (11-1-89), trichlorfon (1I-1-90) and vamidothion (1I-1-91). (2) Antagonists of GABA-regulated chloride channels, such as, for example, cyclodiene organochlorine compounds, such as chlordane (11-2-1) and endosulfan (1I-2-2); or phenylpyrazoles (fiproles), for example ethiprole (1I1-2-3) and fipronil (II-2-4). (3) Sodium channel modulators/voltage-gated sodium channel blockers, such as, for example, pyrethroids, e.g. acrinathrin (11-3-1), allethrin (1I-3-2), a-cis-trans allethrin (1I1-3-3 ), a-trans allethrin (1I-3-4), bifenthrin (1I1-3-5), bioalethrin (1I-3-6), bidsalethrin 5-cyclopentenyl-isomer (11-3-7), bioresmethrin (1I1- 3-8), cycloprothrin (1I-3-9), cyfluthrin (1I-3-10), beta-cyfluthrin (1I-3-11), cygalothrin (1I-3-12), lambda-cyhalothrin (1I-3 -13), gamma-cyhalothrin (1I-3-14), cypermethrin (1I-3-15), alpha-cypermethrin (1I-3-16), beta-cypermethrin (11-3-17), theta-cypermethrin ( 1I1-3-18), zeta-cypermethrin (1I1-3-19), cyphenothrin |(1K)-trans isomers) (1I1-3-20), deltamethrin (1I-3-21), empenthrin E2)-(1K ) isomers) (11-3-22), esfenvalerate (1I-3-23), cefenprox (1I1-3-24), fenpropathrin (1I-3-25), fenvalerate (1I-3-26), flucitrinate (11 -3-27), flumethrin (1I-3-28), tau-fluvalinate (11-3-29), galfenprox (1I-3-30), imiprothrin (11-3-31), cadethrin (1I-3- 32), permethrin (1I-3-33), phenothrin ((1K)-trans i Somerset| (11-3-34), pralethrin (1I-3-35), pyrethrin (pyrethrum) (1I-3-36), resmethrin (1I1-3-37), silafluofen (1I-3-386), tefluthrin (1I -3-39), tetramethrin (1I-3-40), tetramethrin (KE) isomers)| (1I-3-41), tralometrin (1I-3-42) and transfluthrin (11-3-43); or

MOUTH (1I-3-44); or methoxychlor (1I-3-45). (4) Agonists of the nicotinic acetylcholine receptor (NAC), such as, for example, neonicotinoids, such as acetamiprid (1I-4-1), clothianidin (1I-4-2), dinotefuran (1I-4-3), imidacloprid (11- 4-4), nitenpyram (11-4-5), thiacloprid (1I-4-6) and thiamethoxam (1I-4-7); or nicotine (11-4-8). (5) Allosteric activators of the nicotinic acetylcholine receptor (NAC), such as, for example, spinosins, such as spinetoram (1I-5-1) and spinosad (1I1-5-2). (6) Chloride channel activators such as, for example, avermectins/milbemycins, such as abamectin (1I1-6--4), emamectin benzoate (1I-6-2), lepimectin (1I-6-3), and milbemectin (1I- 6-4). (7) Juvenile hormone mimics, such as, for example, juvenile hormone analogs, such as hydroprene (11-7-1), quinoprene (1I-7-2), and methoprene (1I-7-3); or

Zo phenoxycarb (1I-7-4); or pyriproxyfen (1I-7-5). (8) Active compounds with unknown or non-specific mechanisms of action, such as, for example, alkyl halides, such as methyl bromide (11I-8-1) and other alkyl halides; or chlorpicrin (11-8-2); or sulfuryl fluoride (1I-8-3); or borax (1I1-8-4); or potassium antimonyl tartrate (1I1-8-5). (9) Selective antifeedants, such as pymetrozine (11-9-1); or flonicamide (11-9-2). (10) Mite growth inhibitors, such as clofentezine (1I-10-1), hexythiazox (1I-10-2), and diflovidazine (1I-10-3); or etoxazole (II-10-4). (11) Microbial destroyers of the intestinal membrane of insects, e.g.

VasshShiz (Pygipdiepzi5 subspecies Kigeiaki (11-11-4), Vasiyi5 (pygipdiepvi5 subspecies Yepergiopiv (111-11-53) and VT plant protein: StutAb, StutAs, Stgu1!Ra, Stu2AB, teSguzA, StuzAB, StguZzVvVB, Sgu34/35АБИ1 (11 -11- b). (12) Inhibitors of oxidative phosphorylation, ATP breakers, such as, for example, diaphenthiuron (1I1-12-1); or organotin compounds, for example azocyclotin (1I1-12-2), cihexatin (1I-12- 3) and fenbutatin oxide (11-12-4); or propargite (11-12-5); or tetradifon (1I-12-6). (13) Uncouplers of oxidative phosphorylation, which act by interrupting the H proton gradient, such as, for example, chlorfenapyr (11-13-1), OMOS (1I-13-2), and sulfuramide (1I-13-3).(14) Nicotinic acetylcholine receptor antagonists, such as, for example, bensultap (11-14 -1), cartap hydrochloride (II-14-2), thiocyclam (11-14-3) and thiosultap sodium (1I1-14-4). (15) Inhibitors of chitin biosynthesis, type 0, such as, for example, bistrifluron (11-15-1), chlorfluazuron (1I-15-2), diflubenzuron (1I-15-3), flucycloxuron (1I-15-4), flufenoxuron (II-15-5), hexaflumuron (11-15-6), lufenuron (1I-15-7), novaluron (11-15-8), noviflumuron (II-15-9), teflubenzuron (111-15) -10) and triflumuron (II-15-11). (16) Inhibitors of chitin biosynthesis, type 1, such as, for example, buprofezin (II-16-1). (17) Destroyers of molting, dipterans, such as, for example, cyromazine (1I-17-1). (18) Ecdysone receptor agonists such as, for example, chromafenozide (II-18-1), halofenoside bo (11-18-2), methoxyfenoside (II-18-3) and tebufenoside (II1-18-4).

(19) Octopaminergic agonists such as, for example, amitraz (11-19-1). (20) Inhibitors of electron transport through complex I, such as, for example, hydramethylnon (PI-20-1); or acequinocyl (1I1-20-2); or fluacripyrim (1I-20-3). (21) Inhibitors of electron transport through complex I, for example,

METI acaricides such as phenaquine (11-21-1), fenpiroximate (1I-21-2), pyrimidifen (1I1-21-3), pyridaben (11-21-4), tebufenpyrad (1I1-21-5) and tolfenpyrad (1I-21-6); or rotenone (deris) (1I-21-7). (22) Blockers of potential-dependent sodium channels, for example indoxacarb (11-22-1); or metaflumizone (1I1-22-2). (23) Inhibitors of acetyl-CoA carboxylase, such as, for example, tetronic and tetramic acid derivatives, such as spirodiclofen (1I-23-1), spiromesifen (PI-23-2) and spirotetramate (II-23-3). (24) Inhibitors of electron transport through the IM complex, such as, for example, phosphines, such as aluminum phosphide (11-24-1), calcium phosphide (11-24-2), phosphine (1I1-24-3), and zinc phosphide (1I-24-4); or cyanide (11-24-5). (25) Inhibitors of electron transport through the II complex, such as, for example, cyenopyraphen (II-25-1). (28) Ryanodine receptor effectors, such as, for example, diamides, such as chlorantraniliprole (1I-28-1) and rubendiamide (1I-28-2).

Additional active compounds with an unknown mechanism of action, such as, for example, amidoflumet (II-29-1), azadirachtin (1I-29-2), benclothiase (1I-29-3), benzoximate (II-29-4), biphenazate (1I-29-5), bromopropylate (II-29-6), quinomethionate (1I-29-7), cryolite (1I-29-8), cyantraniliprole (ciazipyr) (1I-29-9), cyflumethofen (II -29-10), dicofol (111-29-11), diflovidazine (1I-29-12), fluensulfon (111-29-13), flufenerim (II-29-14), flufiprole (111-29-15) , fluopiram (1II-29-16), fufenozide (111-29-17), imidaclotis (11-29-18), iprodione (1I-29-19), pyridalyl (111-29-20), pyrifluquinazone (1I- 29-21) and iodomethane (I-29-22); in addition, preparations based on VasShiv iptiv (1-1582, Viomeet, Moiimo) (111-29-23), as well as the following known active compounds:

3-bromo-M-(2-bromo-4-chloro-6-Cl-cyclopropylethyl)carbamoyl|phenyl)-1-(3-chloropyridin-2-yl)-1 H-

From pyrazole-5-carboxamide (II-29-24) (known from MUO2005/077934). 4-((6-bromopyrid-3-yl)methyl)(2-fluoroethyl)amino)furan-2(5H)-one (PI-29-25) (known from UUO2007/115644), 4-P(6b- fluoropyrid-3-yl)methyl)(2,2-difluoroethyl)amino)furan-2(5H)-one (1I1-29-26) (known from UMO2007/115644). 4--(2-chloro-1,3-thiazol-5-yl)umethyl|(2-fluoroethyl)amino)furan-2(5H)-one (P-29-27) (known from

MO2007/115644), A-C(6b-chloropyrid-3-yl)methyl|(2-fluoroethyl)amino)furan-2(5H)-one (P-29-28) (known from UMO2007/115644), 4 -(6b-chloropyrid-3-yl)methyl)|(2,2-difluoroethyl)amino)furan-2(5H)-one (1I-29-29) (known from UMO2007/115644), 4-1(6b -chloro-5-fluoropyrid-3-yl)methyl|(methyl)amino)furan-2(5H)-one (P-29-30) (known from UMO2007/115643), 4-((5,6b-dichloropyrid -3-yl)methyl|(2-fluoroethyl)aminofuran-2(5H)-one (1I1-29-31) (known from M/O2007/115646), 4-PC(6b-chloro-5-fluoropyrid-

3-yl)methyl(cyclopropyl)aminofuran-2(5H)-one (1I1-29-32) (known from UMMO2007/115643). 4-(6-chloropyrid-3-yl)methyl|(cyclopropylamino)ufuran-2(5H)-one (111-29-33) (known from EP-A-0 539 588), 4-((6b-chloropyrid -3-yl)methyl|(methyl)aminofuran-2(5H)-one (111-29-34) (known from EP-A-0 539 588),

C1-(6b-chloropyridin-3-yl)/ethylmethyl)oxido-A"-sulfanilidene)cyanamide (1I-29-35) (known (from

UMO2007/149134) and its diastereomers Ш(1K)-1-(b-chloropyridin-Z3-yl)ethyl|("methyl)oxido-A"- sulfanilidene)cyanamide (A) (1I-29-36) and (15 )-1-(b-chloropyridin-3-yl/ethyl|(methyl)oxido-X"-sulfanilidene)cyanamide (B) (11-29-37) (also known from MMO2007/149134) and sulfoxaflor (111-29 -38) (also known from M/O2007/149134) and its diastereomers (((K)-methyl(oxido)(1 K)-1-(6- (trifluoromethyl)pyridin-3-yl|Hiethyl)-X" -sulfanilidenecyanamide (A1) (P1-29-39) and II(5)-methyl(oxido)((15)-1-(6-(trifluoromethyl)pyridin-3-yl|ethyl)-X"-sulfanilidenecyanamide (Ag ) (II-29-40), designated as a group of diastereomers A (known from M/O 2010/074747, MO 2010/074751), (K)-methyl(oxido)((15)-1-(6-«( trifluoromethyl)pyridin-3-yl|Iethyl)-X"-sulfanilidenecyanamide (B1). (1I-29-41) its K5)-methyl(oxido)(1K)-1-I6-(trifluoromethyl)pyridin-3-yl |Hiethyl)-X"-sulfanilidenecyanamide (82) (PI-29-42), designated as a group of diastereomers B (also known from UMO 2010/074747, MO 2010/074751) and 11-(4-chloro-2,6- dimethylphenyl)-12-hydroxy-1 4-dioxa-9-azade spiro|4.2.4.2|)hetradec-11-en-10-one (1I-29-43) (known from MUO2006/089633), 3-(4-fluoro-2,4-dimethylbiphenyl-3-yl)-4 -hydroxy-8-oxa-1-azaspiro(4.5|dec-Z-en-2-one (P-29-44) (known (from

MO2008/067911). 1--2-fluoro-4-methyl-5-(2,2,2-trifluoroethyl)sulfinyl|Ifenyl)-3-(trifluoromethyl)-1H-1,2,4-triazol-5-amine (1I-29 -453 (known from UUO2006/043635), |((35,4аКк,12К,12а5,1255)-3-

Ccyclopropylcarbonyl)oxy|-6,12-dihydroxy-4,12B-dimethyl-11-oxo-9-(pyridin-3-yl)-1,3,4,4a,5,6,ba,12,12a,120 -decahydro-2H,11H-benzo|Ipyrano|4,3-Bchromen-4-yl|methyl bo cyclopropanecarboxylate (II-29-46) (known from ММО2008/066153), 2-cyano-3-(difluoromethoxy)-M , M-

dimethylbenzenesulfonamide (II-29-47) (known from MUMO2006/056433), 2-cyano-3-(difluoromethoxy)-

M-methylbenzenesulfonamide (II-29-48) (known from ММО2006/100288), 2-cyano-3-(difluoromethoxy)-

M-ethylbenzenesulfonamide (1I1-29-49) (known from ММО2005/035486), 4-(difluoromethoxy)-M-ethyl-M-methyl-1,2-benzothiazol-3-amine 1,1-dioxide (1I-29 -50) (known from UMO2007/057407), M-(11-(2,3-dimethylphenyl)-2-(3,5-dimethylphenyl)ethyl|-4,5-dihydro-1,3-thiazol-2- amine (1I-29-51) (known from

MO2008/104503), 1-K2E)-3-(4-chlorophenyl)prop-2-en-1-yl|-5-fluorospiro(indole-3,4-piperidine|- 1(2H)-ylyl2-chloropyridin- 4-ilumethanone (II-29-52) (known from UMO2003/106457), 3-(2,5-dimethylphenyl)-4-hydroxy-8-methoxy-1,8-diazaspiro|4.5|dec-Z-en- 2-on (1I-29-53) (known "(iz

MO2009/049851), 3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-1,68-diazaspiro|4.5|dec-3-en-4-yl ethyl carbonate (PI-29-54) (known from MO2009/049851), 4-(but-2-yn-1-yloxy)-6-(3,5-dimethylpiperidin-1-yl)-5-fluoropyrimidine (1I1-29-55) (known from UMO2004/099160 ), (2,2,3,3,4,4,5,5- octafluoropentyl)(3,3,3-trifluoropropyl)malononitrile (II-29-56) (known from UMO2005/063094), (2,2 ,3,3,4,4,5,5-octafluoropentyl)(3,3,4,4,4-pentafluorobutyl)malononitrile (II-29-57) (known from

MO2005/063094), 8-(2-(cyclopropylmethoxy)-4--trifluoromethyl)phenoxy1|-3-(6- (trifluoromethyl)pyridazin-3-yl|-3-azabicyclo|3.2.|octane (I1I-29- 58) (known from MUMO2007/040280), 2-ethyl-7-methoxy-3-methyl-6-((2,2,3,3-tetrafluoro-2,3-dihydro-1,4-benzodioxin-b- yl)oxy|quinolin-4-yl methyl carbonate (II-29-59) (known from )UR2008/110953), 2-ethyl-7-methoxy-3-methyl-6-(2,2,3,3-tetrafluoro -2,3-dihydro-1,4-benzodioxin-b-yl)oxy|quinolin-4-yl acetate (PI-29-60) (known (from

UR2008/110953), PE1364 (SAB5 reg. Me 12047 76-60-2) (111-29-61) (known from UR2010/018586), 5-(5-(3,5-dichlorophenyl)-5-trifluoromethyl )-4,5-dihydro-1,2-oxazol-3-yl|-2-(1H-1,2,4-triazol-1-yl/benzonitrile (1-29-62) (known from UMO2007/075459 ), 5-(5-(2-chloropyridin-4-yl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazol-3-yl|-2-(1H-1,2,4 -triazol-1-yl)benzonitrile (P1-29-63) (known from UMO2007/075459), 4-I(5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- 1,2-oxazole-

3-yl|-2-methyl-M-(2-oxo-2-((2,2,2-trifluoroethyl)amino|ethyl)benzamide (P1-29-64) (known from MO2005/085216), 4 -C(b-chloropyridin-3-ylmethyl|(cyclopropyl)amino)-1,3-oxazol-2(5H)-one (1I-29-65), 4-(b-chloropyridin-3-ylmethyl)| (2,2-difluoroethyl)amino)-1,3-oxazol-2(5H)-one (1I-29-66), 4-C(6-chloropyridin-3-yl)methyl|(ethyl)amino)- 1,3-oxazol-2(5H)-one (PI-29-67), 4-((6-chloropyridin-3-ylylmethyl)(methyl)amino)-1,3-oxazol-2(5H)-one (1I-29-68) (all known from UMO2010/005692). MMI-0711 (1I-29-69) (known from UMO2002/096882), 1-acetyl-M-I4-(1,1,1,3,3,3-hexafluoro-2-methoxypropane-2-

Zyl)-3-isobutylphenyl|-N-isobutyryl-3,5-dimethyl-1H-pyrazole-4-carboxamide (1I-29-70) (known from

UMO2002/096882), methyl 2-(2-(I3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-ylcarbonyl)amino)-5-chloro-3-methylbenzoyl|-2- methyl hydrazine carboxylate (II-29-71) (known from ММО2005/085216), methyl 2-(2-CI3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-ylcarbonylamino)-5-cyano -3-methylbenzoyl|-2-ethylhydrazinecarboxylate (1I-29-72) (known from UMO2005/085216), methyl 2-(2-(I3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole) -5-ylcarbonylamino)-5-cyano-3-methylbenzoyl|-2-methylhydrazinecarboxylate (II-29-73) (known from M/MO2005/085216), methyl 2-IZ,5-dibromo-2-(3- bromo -1-(3-chloropyridin-2-yl)-1H-pyrazol-5-ylcarbonyl)amino)benzoyl|-1,2-diethylhydrazinecarboxylate (11-29-74) (known from M/O2005/085216), methyl 2 -13,5-dibromo-2-(13-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-ylcarbonyl)amino)benzoyl|-2-ethylhydrazinecarboxylate (P-29-75) ( known from UuUO2005/085216), (52K5,7K5;5K5,75K)-1-(6b-chloro-3-pyridylmethyl)-1,2,3,5,6,7-hexahydro-7-methyl-8-nitro -5-propoxyimidazo|1,2-a|ipyridine (1I-29-76) (known (from

MO2007/101369), 2-16-(2-(5-fluoropyridin-3-yl)-1,3-thiazol-5-yl|pyridin-2-yl)pyrimidine (1I-29-77) (known from M /O2010/006713). 2-16-(2-(pyridin-3-yl)-1,3-thiazol-5-yl|pyridin-2-yl)pyrimidine (1I-29-18) (known from MO2010/006713), 1-( 3-chloropyridin-2-yl)-M-(4-cyano-2-methyl-6-(methylcarbamoyl)phenyl)-3-T5-(trifluoromethyl)-1H-tetrazol-1-yl|methyl)-1H -pyrazole-5-carboxamide (1I-29-79) (known from MMO2010/069502), 1-(3-chloropyridin-2-yl)-M-(4-cyano-2-methyl-6-(methylcarbamoyl)phenyl) |-3-T5-(trifluoromethyl)-2H-tetrazol-2-yl|methyl)-1H-pyrazole-5-carboxamide (1I-29-80) (known from UMO2010/069502), M-(2-( tert-butylcarbamoyl)-4-cyano-6-methylphenyl|-1-(3-chloropyridin-2-yl)-3-C5-(trifluoromethyl)-1H-tetrazol-1-yl|methyl)-1H-pyrazole -5-carboxamide (1I-29-81) (known from UMO2010/069502), M-(2-(tert-butylcarbamoyl)-4-cyano-6-methylphenyl|-1-(3-chloropyridin-2-yl) -3-C5-(trifluoromethyl)-2H-tetrazol-2-yl|methyl)-1H-pyrazole-5-carboxamide (111-29-82) (known from MMO2010/069502) and (1E)-M-( (b-chloropyridin-3-ylylmethyl|-M'-cyano-

M-(2,2-difluoroethyl)ethanimidamide (II-29-83) (known from MMO2008/009360).

Antimicrobial active compounds: (1) Inhibitors of ergosterol biosynthesis, such as aldimorph, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, dodemorph, dodemorph acetate, epoxyconazole, etaconazole, fenarimol, fenbuconazole, phenhexamide, fenpropidine, fenpropimorph , fluquinconazole, flurprimidol, flusilazole, flutriafol, furconazole, furconazole-cis, hexaconazole, imazalil, imazalil sulfate, 60 imibenconazole, ipconazole, metconazole, myclobutanil, naftifin, nuarimol, oxpoconazole,

paclobutrazol, pefurazoate, penconazole, piperaline, prochloraz, propiconazole, prothioconazole, piributicarb, pyrifenox, quinconazole, simeconazole, spiroxamine, tebuconazole, terbinafine, tetraconazole, triadimefon, triadimenol, tridemorph, triflumizole, triforin, triticonazole, uniconazole, uniconazole-r, viniconazole, voriconazole, 1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)ucycloheptanol, methyl 1-(2,2-dimethyl-2,3-dihydro-1H-inden-1 -yl)-1H-imidazole-5-carboxylate,

M'-5-(difluoromethyl)-2-methyl-4-I(3-trimethylsilyl)upropoxy|phenyl)-M-ethyl-M-methylimidoformamide, M-ethyl-M-methyl-M'-(2-methyl -5-(trifluoromethyl)-4-|3-(trimethylsilyl)propoxy|phenyl)imidoformamide and O-(11-(4-methoxyphenoxy)-3,3-dimethylbutan-2-yl|1H-imidazol-1-carbothioate. (2) Respiratory inhibitors (respiratory chain inhibitors), for example, bixafen, boscalid, carboxin, diflumethorim, fenfuram, fluopyr, flutolanil, fluxapiroxad, furametpyr, furmeciclox, isopyrazam - syn-epimer mixture, racemate 1K5,5NK,9K5, and anti- epimer, racemate 1K5,45K,95BK, isopyrazam (anti-epimer, racemate), isopyrazam (anti-epimer, enantiomer 1K,45,95), isopyrazam (anti-epimer, enantiomer 15,4K,9K), isopyrazam (syn- epimer, racemate 1K5,451K,9K5), isopyrazam (syn-epimer, enantiomer 1K,45,9K), isopyrazam (syn-epimer, enantiomer 15,4K,95), mepronil, oxycarboxin, penflufen, pentiopirad, sedaxan, tifluzamide, 1-methyl-M-(2-(1,1,2,2-tetrafluoroethoxy)phenyl|-3-trifluoromethyl)-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-1-methyl-M-( 2 -(1,1,2,2-tetrafluoroethoxy)phenyl|-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-M-(4-fluoro-2-(1,1,2,3,3, 3-hexafluoropropoxy)phenyl|-1-methyl-1H-pyrazole-4-carboxamide and M-(1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl|-3-(difluoromethyl)-1- methyl-1H-pyrazole-4-carboxamide. (3) Respiratory inhibitors (respiratory chain inhibitors) that act on complex III of the respiratory chain, e.g., ametoctradin, amisulbrom, azoxystrobin, cyazofamide, dimoxystrobin, enestroburin, famoxadone, phenamidon, fluoxastrobin, cresoxim-methyl, methominostrobin, orysastrobin, picoxystrobin, pyraclostrobin , pyramethostrobin, pyroxystrobin, pyribencarb, trifloxystrobin, (2E)-2-(2-16-(3-chloro-2-methylphenoxy)-5-fluoropyrimidin-4-yl|oxyphenyl)-2-(methoxyimino)-M-methylethanamide . -M-methyl-2--2-KE)-C1-IZ-"trifluoromethyl)phenyl|ethoxy)imino)methyl|phenyl)ethanamide, (2E)-2-4-2-CІ1Е)-1-(3 -

Zo (E)-1-fluoro-2-phenylethenyl|oxyphenyl)ethylidene|iaminooxy)methyliphenyl)-2-(methoxyimino)-M- methylethanamide, (2E)-2-(2-ICC2E,ZE)-4-(2 ,6-dichlorophenyl)but-3-en-2-ylideneaminooxy)methyl|phenyl)-2-(methoxyimino)-M-methylethanamide, 2-chloro-M-(1,1,3-trimethyl-2,3-dihydro -1H-inden-4-yl)pyridine-3-carboxamide, 5-methoxy-2-methyl-4-(2-CDK1 E)-1-I3- (trifluoromethyl)phenyl|ethylidene)amino)oxy|methyluphenyl)- 2,4-dihydro-ZIN-1,2,4-triazol-3-one, methyl (2E)-2-(2-ICHcyclopropyl|(4-methoxyphenyl)imino|methyl)sulfanyl)methyl|phenyl)-3- Methoxyprop-2-enoate, M-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-(formylamino)-2-hydroxybenzamide, 2-(2-(2,5-dimethylphenoxy)methyl|phenyl)-2 -methoxy-M-methylacetamide and (2K)-2-(2-(2,5-dimethylphenoxy)methyl|phenyl)-2-methoxy-M-methylacetamide. (4) Inhibitors of mitosis and cell division, e.g. benomyl, carbendazim, chlorphenazole, dicefencarb, etaboxam, fluopicolide, fuberidazole, pencicuron, thiabendazole, thiophanate-methyl, thiophanate, zoxamide, 5-chloro-7-(4-methylpiperidine-1- yl)-6-(2,4,6-trifluorophenyl)/1,2,4)griazolo|1,5-a|pyrimidine and 3-chloro-5-(b-chloropyridin-3-yl)-6-methyl -4-(2,4,6-trifluorophenyl)pyridazine. (5) Compounds with multisite activity, e.g., Bordeaux liquid, captafol, captan, chlorothalonil, copper preparations such as copper hydroxide, copper naphthenate, copper oxide, copper oxychloride, copper sulfate, dichlofluanid, dithianone, dodine, dodine free base , ferbam, fluorofolpet, folpet, guazatin, guazatin acetate, iminoctadine, iminoctadine-albesylate, iminoctadine-triacetate, mancopper, mancozeb, maneb, metiram, metiram-zinc, oxin-copper, propamidine, propineb, sulfur and sulfur preparations, for example, polysulfide calcium, thiram, tolylfluanid, zineb and ziram. (6) Resistance inducers such as acibenzolar-5-methyl, isothianil, probenazole and thiadinil. (7) Inhibitors of amino acid and protein biosynthesis, e.g., andoprim, blasticidin-5, cyprodinil, kasugamycin, kasugamycin hydrochloride hydrate, mepanipyrim, and pyrimethanil, (8) Inhibitors of ATP production, e.g., fentin acetate, fentin chloride, fentin hydroxide, and silthiophene. (9) Inhibitors of cell membrane synthesis, such as bentiavalicarb, dimethomorph, flumorph, iprovalicarb, mandipropamide, polyoxins, polyoxorim, validamycin A, and valifenalate. (10) Lipid and membrane synthesis inhibitors, such as biphenyl, chloroneb, dicloran, edifenphos, etridiazole, iodocarb, iprobenphos, isoprothiolane, propamocarb, propamocarb hydrochloride, prothiocarb, pyrazophos, hintosine, tecnazen, and tolclofos-methyl. because (11) Inhibitors of melanin biosynthesis, for example, carpropamide, diclocimeth, phenoxanil,

phthalide, pyroquilon and tricyclazole. (12) Inhibitors of nucleic acid synthesis, such as benalaxyl, benalaxyl-M (kyralaxyl), bupyrimate, clozilacone, dimethyrimole, ethirimol, furalaxyl, himexazole, metalaxyl, metalaxyl-M (mefenoxam), ofuras, oxadixyl, oxolinic acid, (13) Signal transduction inhibitors, such as clozolinate, fenpiclonil, fludioxonil, iprodione, procymidone, quinoxifene, and vinclozolin. (14) Dissociating agents, such as binapacryl, dinocap, ferimzone, fluazinem, and meptyldinocap. (15) Additional compounds such as benthiazole, betoxazine, capsician, carvone, quinomethionate, chalzafenone, kufraneb, cyflufenamide, cymoxanil, cyprosulfamide, dazomet, debacarb, dichlorophen, diclomesin, difenzoquat, difenzoquat methylsulfate, diphenylamine, ecomate, fenpyrazamine, flumethover, fluoromid , flusulfamide, fluthianil, fosetyl-aluminum, fosetyl-calcium, fosetyl-sodium, hexachlorobenzene, irumamycin, metasulfocarb, methyl isothiocyanate, metrafenone, mildiomycin, natamycin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, octylinone, oxamocarb, oxyfenthiin, pentachlorophenol and its salts, phenothrin, phosphoric acid and its salts, propamocarb fosetylate, propanosin sodium, proquinazid, pyrrolnitrin, tebufloquine, tecloftalam, tolnifanid, triazoxide, trichlamid, zarylamide, 1 -(4-14-((5H)-5-(2,6 -difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl|-1,3-thiazol-2-yl)ipiperidin-1-yl)-2-(5-methyl-3-trifluoromethyl) -1 H-pyrazol-1-yl|Iietanone, 1-(4-(4-(55)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl| -1,3-thiazol-2-il upiperidin-1-yl)-2-(5-methyl-3-trifluoromethyl)-1H-pyrazol-1-yl|ethanone, 1-(4-4-15-(2,6-difluorophenyl)-4,5 -dihydro-1,2-oxazol-3-yl|-1,3-thiazol-2-yl)piperidin-1-yl)-2-(5-methyl-3-(trifluoromethyl)-1H-pyrazole-1- yl|ethanone, 1--4-methoxyphenoxy)-3,3-dimethylbutan-2-yl 1n-imidazole-1-carboxylate, 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, 2,3- dibutyl-6-chlorothieno|2,3-4|Ipyrimidin-4(ZH)-one, 2-(5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl|-1-(4-14- ((5HA)-5-phenyl-4,5-dihydro-1,2-oxazol-3-yl|-1,3-thiazol-2-ylpiperidin-1-yl)ethanone, 2-(B-methyl-3 - (trifluoromethyl)-1H-pyrazol-1-yl|-1-(4--4-(55)-5-phenyl-4,5-dihydro-1,2-oxazol-3-yl|-1, 3-thiazol-2-ylpiperidin-1-yl)ethanone, 2-(B-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl|-1-14-(4-(5-phenyl-4, 5-dihydro-1,2-oxazol-3-yl)-1,3-thiazol-2-yl|Ipiperidin-1-yl)iethanone, 2-butoxy-6-iodo-3-propyl-4H-chromene-4 -one, 2-chloro-5-(2-chloro-1-(2,6-difluoro-4-methoxyphenyl)-4-methyl-1H-imidazol-5-yl|pyridine,

Zo 2-phenylphenol and its salts, 3,4,5-trichloropyridin-2,b6-dicarbonitrile, 3-(5-(4-chlorophenyl)-2,3-dimethyl-1,2-oxazolidin-3-yl|pyridine , 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine , 5-amino-1,3,4-thiadiazole-2-thiol, 5-chloro-M'-phenyl-M'-(prop-2-yn-1-iluthiophene-2-sulfonohydrazide, 5-methyl-6- octyl1,2,4|Igriazolo|1,5-a|pyrimidin-7-amine, ethyl (22)-3-amino-2-cyano-3-phenylprop-2-enoate, M-(d-chlorobenzyl)-3 -13-methoxy-4-(prop-2-yn-1-yloxy)phenyl|propanamide, M-Ka-chlorophenyl)(cyano)methyl|-3-13-methoxy-4-(prop-2-yn-1 -yloxy)phenyl|Ipropanamide, M-K5-bromo-3-chloropyridin-2-yl)umethyl|-2,4-dichloropyridin-3-carboxamide, M-P1-(5-bromo-3-chloropyridin-2-yl) )ethyl|-2,4-dichloropyridine-3-carboxamide, M-(1-(5-bromo-3-chloropyridin-2-yl)ethyl|-2-fluoro-4-iodopyridine-3-carboxamide, M-KE )-Kcyclopropylmethoxy)imino||(b-(difluoromethoxy)-2,3- difluorophenyl|methyl)-2-phenylacetamide, M-(2)-Kcyclopropylmethoxy)imino|(b-(difluoromethoxy)-2,3- difluorophenyl| methyl)-2-phenyl cetamide, M-methyl-2-(1-C5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl)acetyl)piperidin-4-yl)-M-(1,2,3,4-tetrahydronaphthalene -1-yl)-1,3-thiazol-4-carboxamide, M-methyl-2-(1-Cb-methyl-3-trifluoromethyl)-1H-pyrazol-1-yl(acetyl)piperidin-4-yl )-M-(1 H)-1,2,3,4-tetrahydronaphthalene-1-yl|-1,3-thiazole-4-carboxamide, M-methyl-2-(1-CP5-methyl-3-( trifluoromethyl)-1H-pyrazol-1-yl|iacetyl)piperidin-4-yl)-M-((15)-1,2,3,4-tetrahydronaphthalen-1-yl|-1,3-thiazol-4 - carboxamide, pentyl 16-41-methyl-1H-tetrazol-5-yl)uphenyl)methylideniaminooxy)methyl|pyridin-2-ylcarbamate, phenazine-i-carboxylic acid, quinoline-8-ol and quinoline-8-ol sulfate (2:1).

All components of the mixtures mentioned in classes (1) - (15) can, if they are able based on their functional groups, optionally form salts with suitable bases or acids. (16) Additional compounds, for example 1-methyl-3-(trifluoromethyl)-N-(2'-(trifluoromethyl)biphenyl-2-yl|-!H-pyrazole-4-carboxamide, M-(4-chlorobiphenyl-2 -yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, M-(2',4"-dichlorobiphenyl-2-yl)-3-(difluoromethyl)-1-methyl- 1 H-pyrazole-4-carboxamide, 3-(difluoromethyl)-1-methyl-M-(4-(trifluoromethyl)biphenyl-2-yl|-1 H-pyrazole-4-carboxamide, M-(2,5- difluorobiphenyl-2-yl)-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-1-methyl-M-(4-(prop-1-yn-1-yl) )biphenyl-2-yl|-1 H-pyrazole-4-carboxamide, 5-fluoro-1,3-dimethyl-M-|4- (prop-1-yn-1-yl)biphenyl-2-yl|- 1 H-pyrazole-4-carboxamide, 2-chloro-M-(4-(prop-1-yn-1-yl)biphenyl-2-yl|pyridin-3-carboxamide, 3-(difluoromethyl)-M-( 4-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl|-1-methyl-1H-pyrazole-4-carboxamide, M-(2-(3,3-dimethylbut-1- yn-1-yl)biphenyl-2-yl|-5-fluoro-1,3-bo dimethyl-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-M-(4-ethynylbiphenyl-2-yl)- 1-methyl-1 H-

pyrazole-4-carboxamide, M-(4-ethynylbiphenyl-2-yl)-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide, 2-chloro-M-(4-ethynylbiphenyl-2-yl) )pyridine-3-carboxamide, 2-chloro-M-(4-(3,3-dimethylbut-1-yn-1-yl)/biphenyl-2-yl|Ipyridine-3-carboxamide, 4-(difluoromethyl)- 2-methyl-M-(4-(trifluoromethyl)biphenyl-2-yl|-A1,3-thiazole-5-carboxamide, 5-fluoro-M-(4-(3-hydroxy-3-methylbut-1-yne) -1-yl)biphenyl-2-yl|-1,3-dimethyl-1H-pyrazole-4-carboxamide, 2-chloro-M-(4-(3-hydroxy-3-methylbut-1-yn-1- yl)biphenyl-2-yl|pyridin-3-carboxamide, 3-(difluoromethyl)-M-(4-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl|-1 - methyl-1H-pyrazole-4-carboxamide, 5-fluoro-M-(4-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl|-1,3-dimethyl- 1H-pyrazole-4-carboxamide, 2-chloro-M-(4-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl|pyridine-3-carboxamide, (5-bromo -2-methoxy-4-methylpyridin-3-yl)(2,3,4-trimethoxy-6-methylphenyl)umethanone and /M-(2-(4-1T3-(4-chlorophenyl)prop-2-yn- 1-yl|oxy-3-methoxyphenyl)ethyl|-Ma2-(methylsulfonyl)valinamide.

The active compounds identified here by their common names are known and described, for example, in the pesticide handbook ("Te Rezvziiside Mapia!" 14th ed., Vgyi5py Stor Rgoiesiyop

Soipsii 2006), or can be found on the Internet (eg pErulimli aiapjos.peiriziisidev).

All components of the mixtures mentioned in classes (1) - (16) can, if they are able based on their functional groups, optionally form salts with suitable bases or acids.

In conclusion, it has been found that the new compounds of formula (I), with good plant tolerance, favorable toxicity relative to homeothermic animals and good environmental compatibility, are suitable, in particular, for the control of animal pests, especially arthropods, insects, arachnids, helminths, nematodes and molluscs that have to be dealt with in agriculture, in forests, in the protection of stored products and materials, and in the field of hygiene, or in the field of veterinary medicine. Compounds according to the invention can similarly be used in the field of veterinary medicine, for example, to combat endo- and or ectoparasites.

Compounds according to the invention can be used as means to combat animal pests, preferably as means to protect agricultural crops. They are effective against pests with normal sensitivity and against resistant species, at all or some stages of development.

Compounds according to the invention can be translated into well-known compositions. In general, such compositions contain from 0.01 to 98 wt.9o of the active compound, preferably from 0.5 to 90 wt.9b5.

The compounds according to the invention can exist in their commercially available compositions and in the forms of use obtained from such compositions, as well as in admixture with other active compounds or synergists. Synergists are compounds that enhance the effect of active compounds, and the added synergist does not necessarily have its own activity.

The content of the active compound in the application forms obtained from commercially available formulations can vary widely. The concentration of the active compound in application forms can be in the range from 0.00000001 to 95 wt.95 of the active compound, preferably from 0.00001 to 1 mabs.95.

Compounds are applied in a conventional manner suitable for the form of application.

The invention can be used for processing all plants and parts of plants. Plants in this context are meant to include all plants and plant populations, such as desirable and undesirable wild plants or cultivated plants (including naturally occurring cultivated plants). Cultivated plants may be plants obtained by traditional methods of breeding and optimization or by means of biotechnological and gene-technological methods, or by means of combinations of these methods, and include transgenic plants, as well as cultivars of plants protected or not protected by rights of plant breeders. Plant parts include all above- and below-ground plant parts and organs such as shoot, leaf, flower and root, examples of which include leaves, needles,

BO stems, trunks, flowers, fruiting bodies, fruits and grain, as well as roots, tubers and rhizomes.

Plant parts also include harvested material and vegetative and generative propagating material, such as petioles, tubers, rhizomes, sprouts, and seeds.

According to the invention, the treatment of plants and plant parts with active compounds is carried out directly or by ensuring their effect on the environment, the place of distribution or the place of storage of plants and plant parts by conventional processing methods, for example by immersion, spraying, evaporation, aerosol irrigation, spreading, painting, spraying and, in the case of propagating material, especially in the case of grain, also by applying one or more coatings.

As mentioned above, all plants and their parts can be processed according to the invention. for In a preferred embodiment, wild plant species and plant cultivars are treated, or those

which are obtained by traditional biological breeding methods, such as crossing or fusion of protoplasts, and their parts. In an additional preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, if necessary in combination with conventional methods (genetically modified organisms), and their parts are processed. The terms "parts" or "plant parts" or "plant parts" have been explained above.

More preferably, according to the invention, the plants of cultivars of plants, each of which is available for purchase or is in use, are processed. Plant cultivars should be understood as plants that have new properties ("characteristic features") and that have been obtained by traditional methods of breeding, mutagenesis or recombinant DNA. They can be cultivars, biotypes and genotypes.

In the field of veterinary medicine, i.e. in the field of veterinary medicine, the active compounds according to the present invention act against animal parasites, especially ectoparasites or endoparasites.

The term "endoparasites" includes, in particular, helminths such as cestodes, nematodes or trematodes, and protozoa such as coccidia. Ectoparasites are typically and predominantly arthropods, in particular, insects, such as flies (stinging and licking), parasitic fly larvae, lice, hair lice, mealybugs, fleas, etc.; or acarids, such as mites, such as hard mites or soft mites, or such mites, such as horse mites, red body mites, bird mites, etc.

It was also found that the compounds according to the invention have a strong insecticidal effect against insects that destroy industrial materials. Industrial materials in this context mean non-living materials, mainly such as plastics, adhesives, glues, paper and cards, leather, wood, wood processing products and coating compositions.

In addition, the combinations according to the invention can be used as antifouling compositions, alone or in combination with other active compounds.

The active compounds are also suitable for the control of vermin in the domestic sector, in the field of hygiene and in the protection of stored products, especially for the control of insects, arachnids and mites that are found in closed spaces, for example in houses, factory premises, offices , vehicle salons, etc. They can be used to control these pests alone or in combination with other active agents

With compounds and auxiliary substances in insecticidal products for home use. They are effective against sensitive and resistant species, and at all stages of development.

Plants include all plant species, plant cultivars and plant populations, such as desirable and undesirable wild plants or cultivated plants. Cultivated plants to be processed according to the invention are plants that occur in nature or plants that are obtained by traditional methods of breeding and optimization or by means of biotechnological and recombinant methods or by combining the methods mentioned above.

The term cultivated plants, of course, also includes transgenic plants.

Plant cultivars should be understood as plants that have new properties (characteristic features) and that were obtained by traditional methods of breeding, mutagenesis or recombinant DNA, or their combination. They can be cultivars, varieties, bio- or genotypes.

Plant parts mean all parts and organs of plants, above-ground and underground, such as shoot, leaf, flower and root, including leaves, needles, peduncles, stems, flowers, fruiting bodies, fruits, grain, roots, tubers and rhizomes. The term plant part also includes collected material and vegetative and generative material for propagation, such as petioles, tubers, rhizomes, sprouts and grain or seeds.

In a preferred embodiment, naturally occurring plant species and plant cultivars, or those obtained by traditional methods of breeding and optimization (eg, crossing or fusion of protoplasts), as well as parts thereof, are processed.

In an additional embodiment according to the invention, transgenic plants obtained by methods of genetic engineering are processed, if necessary, in combination with conventional methods, and their parts.

The processing method according to the invention is preferably used for genetically modified organisms, such as, for example, plants or plant parts.

Genetically modified plants, so-called transgenic plants, are plants in which a heterologous gene has been stably integrated into the genome.

The term "heterologous gene" essentially means a gene that is provided or assembled outside the plant and, when introduced into the nuclear, chloroplast, or mitochondrial genome, confers new or improved agronomic or other properties on the transformed plant by expression of the protein or polypeptide of interest. , or by downregulating or silencing another gene(s) present in the plant (using, for example, antisense techniques, cosuppression techniques, or RNA interference techniques - RNAi).

A heterologous gene located in the genome is also called a transgene. A transgene, which is determined by its specific location in the plant genome, is called a transformational or transgenic event.

Depending on the types of plants or plant cultivars, their location and growing conditions (soil, climate, growing season, nutrition), treatment according to the invention can also lead to additive ("synergistic") actions. Thus, for example, the following actions are possible, exceeding actions that should actually be expected: reduced application rates and/or broadening of the spectrum of activity and/or increased activity of active compounds and compositions that can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or soil moisture or salinity, increased flowering productivity, easier harvesting, accelerated ripening, increased yields, larger fruits, higher plant height, greener leaf color, earlier flowering, increased quality and/or increased nutritional value of harvested products, higher sugar concentration in fruits, better storage stability and/or processing ability of harvested products.

At certain application rates, combinations of active compounds according to the invention also have a strengthening effect on plants. Accordingly, they are also suitable for mobilizing the plant's defense system against the attack of unwanted phytopathogenic fungi and/or microorganisms and/or viruses. This, if necessary, can be one of the reasons for the increased activity of combinations according to the invention, for example, against fungi. Substances that strengthen plants (induce resistance) in this context should be understood as those substances or combinations of substances that are able to stimulate the defense system of plants in such a way that, in the event of future inoculation with undesirable phytopathogenic fungi and/or microorganisms and/or viruses, the treated plants show a significant degree of resistance to these undesirable phytopathogenic fungi and/or microorganisms and/or viruses. In this case, under undesirable phytopathogenic fungi and/or microorganisms and/or viruses, phytopathogenic fungi, bacteria and viruses are meant. Thus, substances according to the invention can be used for protection

From plants against the attack of the above-mentioned pathogens within a specified period of time after treatment.

The time period during which protection is achieved usually lasts from 1 to 10 days, preferably from 1 to 7 days, after treatment of the plants with the active compounds.

Moreover, plants that are preferably treated according to the invention are resistant to one or more biotic stress factors, i.e. said plants have better protection against animals and microbial pests such as nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or or viroids.

In addition to the plants and plant cultivars mentioned above, also suitable for processing according to the invention are those plants that are resistant to one or more abiotic stress factors.

Abiotic stress conditions may include, for example, drought, exposure to low temperature, exposure to heat, osmotic stress, waterlogging, increased soil salinity, increased exposure to minerals, exposure to ozone, exposure to strong light, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, or withdrawal shadows

Plants and plant varieties, which can also be processed according to the invention, are those plants that differ in the characteristics of increased yield. The increased yield of these plants can be the result of, for example, improved plant physiology, improved plant growth and development, such as water use efficiency, water retention efficiency, improved nitrogen utilization, increased carbon assimilation, improved photosynthesis, increased germination efficiency and accelerated ripening. Yield can also be affected by improved plant structure (under stressed and non-stressed conditions), including early flowering, control of flowering for hybrid seed production, seedling vigor, plant size, number and spacing of stem internodes, root growth, seed size, fruit size, pod size , number of pods or ear units, number of seeds per pod or ear, seed weight, increased seed filling, reduced seed dispersal, reduced pod opening and lodging resistance. Additional yield characteristics include seed composition such as carbohydrate content, protein content, oil content and composition, nutritional value, reduced non-nutritive compounds, improved processing ability and better storage stability.

Plants that can be processed according to the invention are hybrid plants that already express the characteristics of heterosis, or hybrid vigor, which usually leads to higher yield, power, health and resistance to biotic and abiotic stress.

Such plants are typically obtained by crossing an inbred parent line with male sterility (maternal form) with another inbred parent line with male fertility (paternal form). Hybrid seed is typically collected from male-sterile plants and sold to agricultural producers. Male-sterile plants can sometimes (e.g., in the case of maize) be produced by panicle pruning (ie, mechanical removal of the male reproductive organs or male flowers), but more typically, male sterility results from genetic determinants in the plant's genome. In that case, and especially when seeds are the target product to be harvested from hybrid plants, it is generally useful to ensure that male fertility in hybrid plants that contain the genetic determinants responsible for male sterility is fully restored. This can be done by ensuring that the parental forms have the appropriate fertility restorer genes that are capable of restoring male fertility in hybrid plants that contain the genetic determinants responsible for male sterility.

Genetic determinants responsible for male sterility may be located in the cytoplasm. Examples of cytoplasmic male sterility (CM5), for example, were described for the species Vgazzis. However, the genetic determinants responsible for male sterility may also reside in the nuclear genome. Male-sterile plants can also be produced using plant biotechnology techniques such as genetic engineering. Particularly suitable methods of obtaining plants with male sterility are described in UUO 89/10396, in which, for example, ribonucleases such as barnase are selectively expressed in tapetum cells in stamens. Fertility can then be restored by expressing a ribonuclease inhibitor such as barstar in the tapetum cells.

Plants or plant cultivars (obtained by means of plant biotechnology methods such as genetic engineering) that can be treated according to the invention are herbicide-tolerant plants, i.e. plants that have been given tolerance to one or more of the given herbicides. Such plants can be obtained either by genetic transformation or by selection of plants containing a mutation that confers such tolerance to herbicides.

Herbicide-tolerant plants are, for example, glyphosate-tolerant plants,

These are plants that have been given tolerance to the herbicide glyphosate or its salt. For example, glyphosate-tolerant plants can be obtained by transforming a plant with a gene encoding the enzyme 5-enolpyruvylshikimate-3-phosphate synthase (ERBRB5). Examples of such genes

ERBRZ is the gene AgoA (mutant ST7) of the bacterium ZaItopeiia yturpitigist, the gene CPA of the bacterium Adgobasietitis 5r., the genes encoding ERBR5 of petunia, ERBRZ5 of tomato, or ERBRZ5 of korakana. EP5P5 can also be mutated. Glyphosate-tolerant plants can also be obtained by expressing the gene encoding the glyphosate oxidoreductase enzyme. Glyphosate-tolerant plants can also be obtained by expressing the gene encoding the glyphosate acetyltransferase enzyme.

Glyphosate-tolerant plants can also be obtained by breeding plants containing natural mutations of the above genes.

Other herbicide-resistant plants are, for example, plants that have been made tolerant to herbicides that inhibit the enzyme glutamine synthase, such as bialaphos, phosphinothricin or glufosinate. Such plants can be obtained by expressing a herbicide detoxifying enzyme or a mutant glutamine synthase enzyme that is resistant to inhibition. One such effective detoxifying enzyme is the enzyme that encodes phosphinothricin acetyltransferase (such as the bug or ray protein from the species Zygeriotusev5). Plants expressing exogenous phosphinothricin acetyltransferase have already been described.

Additional herbicide tolerant plants are also plants that have been given tolerance to herbicides that inhibit the enzyme hydroxyphenylpyruvate dioxygenase (HPDO).

Hydroxyphenylpyruvate dioxygenases are enzymes that catalyze the reaction in which para-hydroxyphenylpyruvate (HPP) is converted to homogenizate. Plants tolerant to inhibitors

HPROs can be transformed with a gene that encodes a naturally occurring stable HPRO enzyme or a gene that encodes a mutated HPRO enzyme. Tolerance to HPPO inhibitors can also be obtained by transforming plants with genes that encode specific enzymes that allow the formation of a homogenizer despite the inhibition of the native HPPO enzyme by the HPPO inhibitor. Plant tolerance to HPPO inhibitors can also be improved by transforming plants with a gene encoding a prephenate dehydrogenase enzyme in addition to a gene encoding a HPPO-tolerant enzyme.

Additional herbicide-resistant plants are plants that have been given tolerance to acetolactate synthase inhibitors (AI 5). Known inhibitors of AG 5 include, for example, herbicides that are derivatives of sulfonylurea, imidazolinone, triazolopyrimidine, pyrimidineoxy(thio)benzoate, or sulfonylaminocarbonyltriazolinone. Different mutations in the enzyme AI 5 (also known as acetohydroxy acid synthase, ANA5) are known to confer tolerance to different herbicides and groups of herbicides. Production of plants tolerant to sulfonylureas and plants tolerant to imidazolinone is described in international publication UMO 1996/033270. Additional plants tolerant to sulfonylurea and imidazolinone were also described, for example, in UMO 2007/024782.

Other plants tolerant to imidazolinone and/or sulfonylurea can be obtained by induced mutagenesis, selection in cell cultures in the presence of herbicide or mutation breeding.

Plants or plant cultivars (produced by plant biotechnology methods such as genetic engineering) that can also be treated according to the invention are insect-resistant transgenic plants, i.e. plants that have been given resistance to attack by specified target insects. Such plants can be obtained by genetic transformation, or by breeding plants containing a mutation that confers such resistance to insects.

In this context, an "insect-resistant transgenic plant" includes any plant containing at least one transgene comprising a coding sequence that encodes: 1) an insecticidal crystal protein from Wasiya5 (hypdiepvi5 or an insecticidal portion thereof, such as insecticidal crystal proteins , described online at: pEr://mmly evsi.iv5zeh.as.ik/Note/Meiy Stisktoge/Vi/, or their insecticidal parts, for example, proteins of the Sgu-protein classes StutAB, StutAs, Stui1E, Stu2ABb, StuZzAe, or StguzvVb , or their insecticidal parts; or 2) a crystal protein from Vasiya5 ИШигипдиепбзизе or its part, which is insecticidal in the presence of a second, other crystal protein from Vasiya5 Ipygipdiepvi5 or its part, such as a binary toxin consisting of crystal proteins SguZ4 and StuZ5; or 3) a hybrid insecticidal protein containing parts of two different insecticidal crystal proteins from Wasiya5 IPygpdiepvib5, such as a hybrid of proteins 1) above, or a hybrid of proteins 2) above, for example, protein StgutA.105, which is produced by the maize event mmOMm89034 (MO 2007/027777); or 4) any one of the above-mentioned proteins 1) - 3), in which several, in particular from 1 to 10,

Amino acids are replaced by another amino acid to obtain higher insecticidal activity against target insect species, and/or to expand the range of target insect species affected, and/or as a result of changes made to the coding DNA during cloning or transformation, such as protein SguzvVB! in maize events MOM863 or MOM88017, or protein

StUZA in the event of May Day of the MICbO4; or 5) an insecticidal secreted protein from VasshShy5 IPyipdiepsie or VasshShiv segei5, or its insecticidal part, such as vegetative insecticidal proteins (MIR), listed in: pEr://mmly evsi.iv5zeh.as.ik/Note/Meiy Stisktoge/Vi/ mir.piti, for example, proteins from the class of proteins

MIRZAa; or b) a secreted protein from Vasilia5 Ipygypdieppi5 or Vasiya5 segei5 that is insecticidal in the presence of a second secreted protein from Vasiya5 (pygypdiepoi5 or B. segetsi5, such as a binary toxin consisting of the crystal proteins MIRTA and MIRA; 7) a hybrid insecticidal protein that contains parts from various secreted proteins from Wasiya5

Iihipdiepvi5 or Vasiyi5 segets5, such as a hybrid of the above-mentioned proteins 1) or a hybrid of the above-mentioned proteins 2); or 8) any one of the above-mentioned proteins 1) - 3), in which several, in particular from 1 to 10, amino acids are replaced by another amino acid to obtain a higher insecticidal activity in relation to the target insect species, and/or to expand the range of target insect species affected and/or as a result of changes made to the coding DNA during cloning or transformation (even though it still encodes an insecticidal protein), such as the MRZAa protein in the cotton event SOT102.

Obviously, an insect-resistant transgenic plant, in this context, also includes any plant containing a combination of genes that encode proteins of any of the above classes 1 - 8. In one embodiment, the insect-resistant plant contains more than one a transgene that encodes a protein of any of the above classes 1 - 8, to expand the range of target insect species affected, or to delay the development of insect resistance to plants, using different proteins that are insecticidal to the same target insect species, but have a different mode of action, for example, binding to different receptor-binding sites in insects.

Plants or plant cultivars (obtained by means of plant biotechnology, such as genetic engineering) that can also be treated according to the invention are tolerant to abiotic stress. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation that provides such stress resistance. Particularly suitable stress-tolerant plants include: a. plants that contain a transgene capable of reducing the expression and/or activity of the poly(ADP-ribose) polymerase (PAPP) gene in plant cells or plants; r. plants that contain a stress-tolerance-enhancing transgene capable of reducing the expression and/or activity of cancer-encoding genes of plants or plant cells; with. plants that contain a stress-tolerance-enhancing transgene that encodes an enzyme of the metabolic pathway of nicotinamide adenine dinucleotide reductive synthesis that is functionally important for plants, including nicotinamidase, nicotinate phosphoribosyltransferase, (nicotinic acid) mononucleotide adenyltransferase, nicotinamide adenine dinucleotide synthetase, or nicotinamide phosphoribosyltransferase.

Plants or plant varieties (obtained by means of plant biotechnology methods such as genetic engineering) which can also be processed according to the invention show altered quantity, quality and/or storage stability of harvested products and/or altered properties of specific ingredients of the harvested as a crop of products, such as, for example: 1) transgenic plants that synthesize modified starch, which according to its physicochemical characteristics, in particular, according to the content of amylose or the ratio of amylose/amylopectin, according to the degree of branching, according to the average value of the chain length, according to the distribution side chains, viscosity characteristics, gelling strength, starch grain size and/or starch grain morphology, altered compared to starch synthesized in plant cells or wild-type plants, so that it is more suitable for special applications. 2) transgenic plants that synthesize non-starch carbohydrate polymers or that synthesize non-starch carbohydrate polymers with altered properties compared to wild-type plants without genetic modification. Examples are plants that produce polyfructose, especially inulin- and levan-types, plants that produce alpha-1,4-glucans, plants that produce alpha-1,6-branched alpha-1,4-glucans, and plants which produce alternan. 3) transgenic plants that produce hyaluronan.

Plants or plant cultivars (obtained by means of plant biotechnology, such as genetic engineering) that may also be processed according to the invention include plants such as cotton with altered fiber characteristics. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation that provides such altered fiber characteristics and include: a) plants, such as cotton, containing an altered form of cellulose synthase genes;

B) plants, such as cotton, containing a modified form of g5m/2 or hem/3 homologous nucleic acids; c) plants, such as cotton, with increased expression of sucrose phosphate synthase; a) plants, such as cotton, with increased expression of sucrose synthase; e) plants, such as cotton, in which the time regulation of the permeability of the plasmodesma at the base of the fiber cell is changed, for example by means of down-regulation of fiber-selective B-1,3-glucanase;

I) plants, such as cotton, that have fibers with altered reactivity, for example through expression of the M-acetylglucosaminetransferase gene, including poas and chitin synthase genes.

Plants or plant cultivars (which may be obtained by means of plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants such as oilseed rape or Vgazvzis family plants with altered oil profile characteristics. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation that confers such altered oil profile characteristics and include: a) plants such as rapeseed plants that produce oil with a high oleic acid content;

B) plants, such as oilseed rape plants, which produce oil with a low content of linolenic acid; c) plants such as rapeseed plants that produce oil with a low level of saturated fatty acids.

Particularly suitable transgenic plants that can be processed according to the invention are plants that contain one or more genes that encode one or more toxins, and are transgenic plants that are available under the following trade names: ME O 60 aABO?" ( e.g., corn, cotton, soybeans), KposkOshi" (e.g., corn), Wiesaga?

(for example, corn), VT-Higa" (for example, corn), Zag ipk? (for example, corn), Voiidaga? (cotton),

Misoip? (cotton), Mysoip 338? (cotton), Maishgesaga? (e.g. corn), Rgoiesia? and

Mem/ wai? (potato). Examples of herbicide tolerant plants that should be mentioned are corn, cotton, and soybean cultivars available under the following trade names: Coipair Keadu? (tolerance to glyphosate, eg corn, cotton, soybean), Gibepu Hipk? (tolerance to phosphinothricin, such as oilseed rape), IMI? (tolerance to imidazolinone) and 5C52 (tolerance to sulfonylurea, for example corn).

Herbicide-resistant plants (plants conventionally bred for tolerance to herbicides) that may be mentioned include varieties that are available under the name

SiIvaptei!a? (for example, corn).

Particularly suitable transgenic plants that can be processed in accordance with the invention are plants that contain transformation events, or a combination of transformation events, and which are listed, for example, in the databases of various national or regional government regulatory bodies (see, for example, pEr: /dptoipo.|gs.y/dtr rgom/use.azrh. and pEruLlimly.adbioz.sot/abaze.rpr).

Treatment according to the invention of plants and plant parts with a combination of active compounds is carried out directly or by ensuring the effect of the compounds on the environment, the place of their growth or the place of storage by conventional processing methods, for example by immersion, spraying, evaporation, aerosol irrigation, spreading, painting and, in the case of propagating material, particularly in the case of grain, also by applying one or more coatings.

The mixtures according to the invention are particularly suitable for seed treatment. Here, the combinations according to the invention mentioned above can be separately mentioned as better or especially better. Thus, most of the damage to cultivated plants, which is caused by pests, occurs when the seeds are invaded during storage and after placing the seeds in the soil, as well as during and immediately after the germination of plants. This phase is particularly important because the roots and shoots of a growing plant are particularly sensitive and even a slight damage can lead to the death of the entire plant. In this regard, the protection of seeds and germinating plants using suitable compositions is of particular interest.

Co) Pest control by means of plant seed treatment has been known for a long time and is subject to constant improvement. However, seed processing involves a number of problems that cannot always be solved satisfactorily. Thus, it is desirable to develop methods of protecting seeds and germinating plants, which do without additional application of compositions for the protection of agricultural crops after sowing or after emergence of plants. In addition, it is desirable to optimize the amount of the active compound used in such a way as to ensure optimal protection of the seeds and germinating plants from the attack of pests, but without damaging the plant itself with the active compound used. In particular, methods of seed treatment should also take into account the inherent insecticidal properties of transgenic plants in order to achieve optimal protection of seeds and germinating plants, while using a minimum number of compositions for the protection of agricultural crops.

Therefore, the present invention, in particular, also relates to a method of protecting seeds and germinating plants from pest attack by treating seeds with a composition according to the invention. The invention similarly relates to the use of compositions according to the invention for treating seeds to protect seeds and plants growing from them against pests.

The invention further relates to seeds that are treated with a composition according to the invention for protection against pests.

One of the advantages of this invention is that the special system properties of the compositions according to the invention provide that the treatment of seeds with these compositions protects not only the seeds themselves, but also those formed after the germination of the plant from pests. In this way, it is possible to do without direct processing of the crop during sowing or soon after it.

Another advantage is the synergistically increased insecticidal activity of the compositions according to the invention in comparison with a separate insecticidally active compound, which exceeds the expected activity of two active compounds when they are applied separately. It is also beneficial to synergistically increase the fungicidal activity of the compositions according to the invention in comparison with a single fungicidally active compound, which exceeds the expected activity of the active compound applied alone. This allows optimization of the number of active compounds used.

In addition, it should be considered useful that the mixtures according to the invention, in particular, can also be used for the treatment of transgenic seeds, where the plants emerging from these seeds are able to express a protein directed against pests. By treating such seeds with compositions according to the invention, certain pests can be controlled only by expression of, for example, an insecticidal protein, and seed damage can be additionally prevented using compositions according to the invention.

The compositions according to the invention are suitable for protecting the seeds of any kind of plants, as already mentioned above, which are used in agriculture, in greenhouses, in forests or in horticulture. In particular, such seeds are the seeds of corn, peanuts, canola, rapeseed, poppy seeds, cultivated soybeans, cotton, beets (for example, sugar beets and fodder beets), rice, millet, wheat, barley, oats, rye, sunflower, tobacco, potatoes or vegetables (for example, types of tomatoes, cabbage). The compositions according to the invention are similarly suitable for treating the seeds of fruit plants and vegetables, as already mentioned above.

Treatment of corn, soybeans, cotton, wheat and canola or rapeseed seeds is particularly important.

As already mentioned above, the treatment of transgenic seeds with the composition according to the invention is also of particular importance. Such seeds are the seeds of plants, which, as a rule, contain at least one heterologous gene that controls the expression of a polypeptide, in particular, with insecticidal properties. In this context, heterologous genes in transgenic seeds can be obtained from microorganisms such as Vasiin5, Kpi2obisht, Rzeidotopav, 5eitaia,

Tiispodegta, Siamirasieg, Siotiv5 or Siyosiadiysht. The present invention is particularly suitable for processing transgenic seeds that contain at least one heterologous gene derived from

Wasyiv 5 years, and whose gene product shows activity against the corn moth and/or long-bearded flea. The involved gene is more preferably a heterologous gene derived from Vasiyv5

Iipdiepviv.

In the context of this invention, the compositions according to the invention are applied to the seeds either by themselves or in a suitable composition. Preferably, the seed is processed in a state in which it is sufficiently stable to avoid damage during processing. In general, seed can be treated at any time between harvest and planting. The seeds are usually used in a form separated from the plant and free from cobs, grain shells, flower stalks, skin, villi or fruit pulp.

Of course, when treating the seeds, it must be ensured that the amount of the composition according to the invention applied to the seeds and/or the amount of additional additives is such that it does not lead to disruption of seed germination or damage to the resulting plants. This must be ensured especially in the case of active compounds that can exhibit phytotoxic effects at certain application rates.

In addition, the compounds of the invention can be used to control a variety of pests, including, for example, harmful sucking insects, stinging insects and other pests that ARE plant parasites, pests of stored materials, pests that destroy industrial materials, and pests in the field of hygiene, including parasites in the field of veterinary medicine, for example, for their destruction and elimination. Thus, the present invention also includes pest control methods.

In the field of veterinary medicine, i.e. in the field of veterinary medicine, the active compounds according to this invention act against animal parasites, especially ectoparasites or endoparasites.

The term "endoparasites" includes, in particular, helminths such as cestodes, nematodes or trematodes, and protozoa such as coccidia. Ectoparasites are usually and mainly arthropods, especially insects, such as flies (stinging and licking), parasitic fly larvae, lice, hair lice, mealybugs, fleas, etc.; or acaricides such as ticks, such as hard ticks or soft ticks, or ticks such as horse ticks, red body ticks, bird ticks, etc.

These parasites include:

From the Aporishigida series, for example, Naetaiioripiv5 5yr., Hypodpayiz 5yr., Redisshiv5 5yr., RAPigi5 5yr. and bBoIeporoie5 5yr.; special examples are: I ipodpaifyi»v5 5eyo5i5, I ipodpaiyiv5 mishii,

Mpodpashiv omiyy5, And ipodpaiiiv omiiogptibh, And ipodpaiiivye redai5, Iipodpaiiiv v5ivporviv,

Naetaiioripiv avipi tasgtoserna|sh5, Naetaiioripye eshshuvietiv, Naeetaiioripye 5itsy5, Redisshiv pPytapyv sariyivyh, Redisshiv Nytapyv sogrogiz, Rnuioegta mabviayih, Horn of fishes, bZoieporoiev5 sariiyatv;

From the MaiyshPorpacdidcha series and the Atriusegipa and Izspposegipa suborders, for example, Tgiteporop 5yr.,

Meporop 5 years, GPipoiop 5 years, Vomisoia 5 years, M/egpeskKieia 5 years, I eriKepitop 5 years, Satayina 5 years,

Tgispodesiez 5 years. and Reiisoia 5 years; special examples are: Vomisoia romi5, Vomisoia omi5, Vomisoia

Itvaia, the bataina of the Roma, Tispodesia5 of the saps, Reiissoia zirgovzigaishv5, Vomisoia sargae, And erikepigtop of the Omiv,

Megteskivyia edii;

From the Oiriega series and suborders of Metaiosegip and Vgaspusegip, for example, Aedez 5yr., Aporpeiez 5yr., 60 Sekh 5yr., Bitiysht yr., EivitiyySht yr., Rpieroiotiv 5yr., I shgotuia 5yr., Siisoide 5yr.,

Spguzor5 year.

Najetaioroia v5yrs., RNyirotuia 5yrs., Vgatssia 5yrs., Myvsa 5yrs., Nuagoiaea 5yrs., Ziotochuv 5yrs.,

Najetayorbia 5yrs., Mogeia z5yrs., Rappia 5yrs., Siozzipa 5yrs., Saiirnoga 5yrs., I isiia v5yrs., Snpguzotuia 5yrs., UMopIannia 5yrs., Zagsorpada 5yrs., Oevipy5 yrs., Nurodepta 5yrs.

Nirrorozsa 5 years, Iiroriepa 5 years, Meiorpady 5 years, Kpipoevzigi 5 years, Tirsha 5 years; special examples are: Aede5 aeedurii, Aede5 aiYirorisii5, Aede5 Iaepiotupspiv, Aporpeiez datriae,

Aporpeie5 tasiiiireppiv, Saiiiirpoga eguipgosernaiia, SNguzo2opa rishimiaiv5, Sceh diipdiegavsiaiviv,

Seh ririepv, Scieh iagzaii5, Rappia sapisciagi5, Zagsornada sagtaipa, 5iotokhuv saisiiigap5, Tirsha raishdosa, I isiia syrgipa, I isiia zegisaia, bitiyisht geriap5, Rpieroiotivh raraiavzi, RimTeroyutiv

Iopdira|Irii, Odadtia ogpaia, U/iNeitia edtsipa, Voorpiyoga eguiigosernaia, Tabapiv Brgotiv,

Tabapiz zrodoriegy5, Tarapyv angashv, Tarapyv 5tsaeeyiiysiv, Nurotiyiga siigea, Spguzor5 sayesciepv,

SNguzorz geiiistiv5, Naetaiyoroya rishmiaiv5, Naetaiyoroya aiisa, Mizsa ashitpai»v, Myvsa dotevziisa,

Naetaigjorbia ityap5 ityap5, Naetayiobia itytap5 echidna, Naetayyobia 5iytshiapv, Nuagoyaea ityapv,

Nuayugava aiibiripsia, Snguzotua sPiogoruda, Spguzotua reg7iapa, Oyezigi5 omi5, Nurodepta romiv,

Nurodetta Ipeasht, Ri2pemai!5Kiapa 5iepih, YuOeptaiobia potipih5, Meiornadiv omipyv, Iiroriepa sargeoii, IIroriepa seg, Nirrorozsa magiedaia, Nirrorozsa edshiipa, Saviegornishv5 ipieviipaiiv,

Saviegorniy5 Naeto!toiidaiyi5, Saviegornpishv5 ipegtiv, Saviegornishv5 pazaiiv, Szaziegorpii5 podgisogpiv,

Saviegorniysh5 resogyt, Vgashtsia soyesa;

From the series of Zirpoparieegida, for example Ryeh 5yr., Steposerpaiide5 yr., Tipda 5yr., HeporzuPNa 5yr., Segaorpuii5 yr.; special examples are: SieposerpPaiide5 sapi5, Steposerpaiidez Teii5,

Riieh ittapv, Tipda repeigapo, Heporzuia speoriv;

From the Neiegoriegid series, for example, Sitekh 5yr., Tiayuta 5yr., Kpoapiiv 5yr. and Rapzigopoduiy5 5yr.

From the Viatsagida series, for example Viatsa ogiepiai5, Regiriapega ategisapa, Viatseia degtapisa and zireia 5rr. (for example, Z,irreia Iopadira!ra);

From the Asagi subclass (Asagipa) and Meia- and Mesoziidtaga series, for example, Agdaz 5yr., Ogpipodogiv 5yr., Oyuyubiiz 5yr., Yihodez 5yr., Atbiuotta z5yr., VNirisernaniz (Voorpishv) vyr., Oyeptasepiog 5yr.,

Naetorpuzaii5 5yrs., Nuaiotta 5yrs., Oegtapuzziz 5yrs., KPiriserpa|iv5 5yrs. (the parent genus of ticks that parasitize many hosts), Ogpypopubzbzyb5 5yr., Rpestopuzzyv5 5yr., Kaiieia 5yr.,

Rpeitopuzzyv z5yr., 5ietposiota 5yr., Maitoa 5yr., Asagari5 5yr.; specific examples are:

Zo Agaa5 regzisiv, Aghdaz gePyekhiv, Ogpiyipodogi5 toibaia, Otobiy5 teodpipi, VNiriserna!n5 (Vornpish5) tisgtoriye, APiriserpa!nbv (Vorpiysh5) aesoiogaish5, NApPiriserna!e (Vorpyi5) appshatsiv,

ВПірісерпа!шв (Воорпіїи5) саЇсегав, Нуатта апаїйоїїсит, Нуатта аєдуріїсит, Нуаїтта тагдіпайт, Нуаотта ігапзівеп5, РВПірісерНна|в5 еменпіві, Їходев5 гісіпи5, Їходе5 пехадопивх, Їходев5 сапізида, Іходез ріювзив, Їходе5 гибісипдив, Їходе5 5саршціагі5, Їїходе5 ПпоЇосусіи5, Наетарпузаїї5 сопсіппа, Наетарпузаїї5 ripsiaia, Naeeetarpnuzaivb sippabagipa, Naeeetarpnuzaiiv oyurnia,

Naetarpuzai5 Ieasni, Naetarpnuzaiiv Iopdisoti, Oeptasepiog tagdipai5, Oegtasepog geiiisshativ,

Oeptasepiog risii5, YuOeptasepiuog aiBirisii5, YuOeptasepiog apadegzopi, YuOeptasepiog maipabiiv,

Nuatta tashtyapisit, EPiriserpaie zapdtsipei5, RPiriserpa!b5 Bigza, NAPirisernaiv5 arrepaisciatv, APirisernav sarepvib5, NPiriserpanv Shshtgapisiv5, APiriserpaiv 2atreliepviv,

AtbBiuotta ategisapit, Atriuotta magiedite, Atbiuotta tasshasht, Atbriuotta Pebgaeit,

Atbriuotta sa|ieppepzie, Yueptapuvzziv daiyiyipaye, Ogpyiopuzzyv Bigza, Ogpipopuzziv zumiagit,

Maitoa iasorzopi;

From the series of Asiipedida (Rgoziidtagtsa) and Asagidida (Avidtagtsa), for example, Asagariv 5yr., SpeuieyeiPa 5yr., OtyShiospeuieiia 5yr., Muobria v5yr., Rzogegdaie5z vrr., YuOetodeh v5yr., Tgtotbisshia 5yr.,

Iivtorpohyv 5yr., Asagi 5yr., Tugornadyv 5yr., Saiodiurpykh yr., Nurodesievs yr., Riegoiispy 5yr., Rzohoriez yr., SPogiorieez yr., Opodesiez yr., Zagsoriez yr., Moioeyegev yr.,

Kpetidosorie5 5yr., Suodiike5 5yr. and I atipovzioriee5 5yr.; special examples are: SpeuieyeiPa uazdygi, SpeuieiieYia BriaKei, Oetodekh sapih, YuOetodekh romi5, Oetodekh omiz, Oetodekh sargaye,

Retodekh edii, Oetodekh savaii, Oetodekh 5ytsi5, Meoigotrissha ashitnpaiiiv, Meoigotrisshia desaieti,

Meozspopadavziia hegoipeptobvria, Totbissha aKkativeni, Oyudesie5 supoiii5, Moioyeagez saiii, Zagsoriyev sapie, Zagsoriyev5 romiv, Zagsoriyevz omi5, Zagsoriez girisargaeee (-5. sargaye), Zagsoriyevs edii,

Zagsorie5 ztsiv, Reogoriev omi5, Reogorievz sipistii, Reogoriez edii, Spogioriez romi5, Rzoegdaiev omi5, Rpestopuzzoidis tapde, Rpestopuvzzoidez5 sapipit, Asagariv zhmoodi.

The active compounds according to the invention are also suitable for combating arthropods, helminths and protozoan organisms that attack animals. Animals include farm animals such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, farmed fish, honey bees. Animals also include pets - also called companion animals - such as dogs, cats, caged birds, aquarium fish, and 60 animals known as laboratory animals, such as hamsters, guinea pigs, rats and mice.

The fight against these arthropods, helminths and/or protozoa should reduce mortality and increase productivity (production of meat, milk, wool, skins, eggs, honey, etc.), and improve the health of the host animal. and, accordingly, the use of active compounds according to the invention makes it possible to achieve more economically sound and simple animal husbandry.

For example, it is desirable to prevent or interrupt the parasite's consumption of the host's blood (if necessary). Parasite control can also help prevent the transfer of infectious substances.

The term "control" in this veterinary context means that the active compounds act by reducing the manifestations of the parasite in question in an animal infested with such parasites to a safe level. More specifically, "control" in this context means that the active compound destroys the parasite in question, slows its growth or inhibits its reproduction.

In general, the active compounds according to the invention can be used directly when they are used to treat animals. They are preferably used in the form of pharmaceutical compositions, which may contain pharmaceutically acceptable fillers and/or excipients known in the art.

In the field of veterinary medicine and in animal husbandry, active compounds are used (administered) in a known way, by enteral administration in the form of, for example, tablets, capsules, drinks, preparations for infusion, granules, pastes, balls, preparations for administration through a tube and suppositories, using parenteral administration, for example by injection (including intramuscular, subcutaneous, intravenous, intraperitoneal), implants, nasal administration, dermal application in the form of, for example, immersion or bathing, spraying, dousing and spot application, washing and dusting, and by means of molded products containing the active compound, such as collars, ear tags, tail tags, limb bandages, halters, marking devices, etc. The active compounds may be formulated as a shampoo or as suitable formulations applied in aerosols or sprays that are not under pressure, such as in atomizers and sprayers.

In the case of use for livestock, poultry, pets, etc., the active compounds according to the invention can be used in the form of formulations

Zo (for example, powders, wettable powders |"M/R"), emulsions, emulsifying concentrates

HES"), loose compositions, homogeneous solutions and suspension concentrates |"ЗС"|), which contain active compounds in an amount from 1 to 80 wt.95, directly or after dilution (for example, 100-10,000-fold dilution), or they can be used in the form of a chemical bath.

In the case of application in the field of veterinary medicine, active compounds according to the invention can be used in combination with suitable synergists or other active compounds, for example, acaricides, insecticides, anthelmintics, antiprotozoal agents.

The compounds according to the invention can be prepared using conventional methods known to those skilled in the art.

Reaction scheme 1 shows the general method of obtaining A compounds (I) according to the invention.

Reaction scheme 1 ' in! t not nya M vk A

A 8 A 5 - and M

AT, asknya, A ZA, same UA de

A I x app Ar M. o ; more

Az A Adi Mo m td M Az (1) IEA; (FU

Radicals A:-Ah, C), MU, B" and 2" have the meanings described above. T means the group

1 2

And H

M

1z where the radicals 2, 72 and 73 have the values given above, and the asterisk means the point of joining the C-MU group. X stands for any leaving group.

Compounds according to the invention of type (I) can be obtained by the reaction of amines of the general structure (IM) with activated carboxylic acid derivatives of the general structure (M). The reaction can be carried out in the presence or absence of a solvent. At this stage, it is also possible to use a suitable base.

In general, it is advisable to carry out the first stage of the reaction of the method of preparation A according to the invention, if necessary, in the presence of a suitable diluent and, if necessary, in the presence of a suitable basic substance that promotes the reaction.

Diluents are preferably used in such quantities that the reaction mixture remains easily mixed throughout the process.

Any solvent that does not interfere with the reaction, such as, for example, water, is suitable for use as a solvent. Aromatic hydrocarbons such as benzene or toluene are suitable; halogenated hydrocarbons such as dichloromethane, chloroform or carbon tetrachloride, open-chain or cyclic ethers such as diethyl ether, dioxane, tetrahydrofuran or 1,2-dimethoxyethane; esters such as ethyl acetate and butyl acetate; ketones such as, for example, acetone, methyl isobutyl ketone and cyclohexanone; amides such as dimethylformamide and dimethylacetamide; nitriles such as acetonitrile; and other inert solvents, such as 1,3-dimethyl-2-imidazolidinone; solvents can be used individually or in the form of a combination of two or more solvents.

The base used may be an organic base such as triethylamine, ethyldiisopropylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; in addition, it is possible to use, for example, the following bases: hydroxides of alkali metals, such as, for example, sodium hydroxide and potassium hydroxide; carbonates such as sodium bicarbonate and potassium carbonate; phosphates such as potassium hydroorthophosphate and sodium orthophosphate; alkali metal hydrides such as sodium hydride; alkali metal alcoholates, such as sodium methylate and sodium ethylate. These bases can be used relative to compounds (IM) and (M) at ratios of their molar equivalents

From 0.01 to 5.0. In addition, it is also possible to use silver(I) cyanide as a base and activator

YuShoshtai oi Ogdapis Spetivigu. 1992, 57, 4394-4400; doshgpay oi Medisipa! Spetivigu 1992, 35, 3905-3918; Children of Ogdapis Snetivigu 2003, 68, 1843-1851.

The suitable reaction temperature is in the range from -20 "С to the boiling point of the considered solvent, and the reaction time is from a few minutes to 96 hours, depending on the selected reagents, solvents and reaction temperature.

Cyclic carbonyl halides represented by the general structure (M) can be obtained in a simple way by the reaction of heterocyclic carboxylic acid with halogenating reagents, such as thionyl chloride, thionyl bromide, phosphoryl chloride, oxalyl chloride, phosphorus trichloride, etc. (Noirep-MUUEUi, 1952, vol. MI, p. 463 et seq.|.

However, the preparation of carboxamides represented by formula (I) can also be carried out using coupling reagents such as dicyclohexylcarbodiimide and additives such as 1-hydroxybenzotriazole|SPpet. Veg 1970, 788). It is also possible to use coupling reagents such as 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1,1"-carbonyl-1H-imidazole and similar compounds.

Coupling reagents used to carry out the method of preparation are all reagents that are suitable for the formation of an ester or amide bond (cf., for example,

Voaapzku et al., Reriide Zupipeviv, 2nd ed., UMieu 5 op, New York, 1976; Sgo55, Meyeppoieg, Tpe

Reriide: Apaiuziz, Zupipevzi5, Vioiodou, Asadetis Rgez5, New York, 1979).

In addition, for obtaining (I), it is also possible to use mixed anhydrides (U. At. Spet. os 1967, 50121. In this method, it is possible to use various complex esters of chloroformic acid, for example, isobutyl chloroformate, isopropyl chloroformate. Similarly, for this purpose, it is possible to use diethylacetyl chloride, trimethylacetyl chloride, etc.

Compounds of the general structure (IM) can be obtained by the reaction of an amine of the general structure (II) with activated derivatives of a carboxylic acid of the general structure (II). Here, the same conditions as in the preparation of (I) described above are applicable regarding the choice of solvent, reaction conditions, reaction time and reagents.

Reaction scheme 2 shows the general method of obtaining B for the synthesis of compounds (I) according to the invention.

Scheme of the reaction 2 1 -V Ts H

NM SHI! ! in

And tyu Um Zno

A;ZA, x A A -- -ya B: --5 A HA earlier A po

With Ar du a on

M Az AK z (MI) M M (MI-1) (MI)

AND

1 v' Ak sha a-MmNE MOM

II A

AND

A AK M A JAK x

Ai Ge) 2 Az

M

(|) M (WE)

Radicals A:-Ah, O, B', Ne and M/ have the meanings described above. X represents any leaving group and AIK represents an alkyl radical such as, for example, methyl or ethyl. T means group 1 2

AND

M. j

M

1z where the radicals 7, 72 and 73 have the values given above, and the asterisk means the joining point to the C-MU group.

Compounds according to the invention of type (I) can be obtained by the reaction of an amine of the general structure (III) with activated derivatives of a carboxylic acid of the general structure (MI). Here, the same conditions as in the conversion of (IM) and (M) to (I) described in Preparation A are applicable regarding the choice of solvent, reaction conditions, reaction times and reagents.

Activated carboxylic acid derivatives of the general structure (MI) can be obtained by two-step synthesis from the corresponding esters of carboxylic acids of the general structure (MI).

At the first stage, from the function of the carboxylic acid, protected in the form of a complex ether (O-AC), the compound (MII), depending on the complex alkyl ether used, is deprotected with a suitable reagent ., R. b. M. Umtsi5, T.

MU. Sgeepe, Wopp Umieu 5 5op5, Ips., NoroCap, NJ, and the resulting free hydroxyl group of the acid function (MI-1) is converted to the leaving group X. Here, you can use the same methods as already described for obtaining (M). Compounds of the general structure (MI) can be obtained by the reaction of amines of the general structure (MI) with activated carboxylic acid derivatives of the general structure (M). Here, the same conditions as in synthesis (1),

As described in Preparation A, applicable solvent selection, reaction conditions, reaction time, and reagents.

The scheme of reaction C shows the general method of obtaining C of the synthesis of compounds (I) according to the invention.

Scheme of the reaction Z

And in!

And IV-X A

AND; TA, V -O-- A; TA, in

Ii A 2 M.

Mira et Ge)

M M

(41) (I)

The radicals А/:-Ах, 0, Ве and М/ have the values described above. X represents any leaving group such as, for example, chlorine, bromine or iodine. T means group 1 2

AND

M. Kh

M

1z where the radicals 7, 72 and 73 have the values given above, and the asterisk means the joining point to the C-MU group. IN! means the radicals described above, excluding hydrogen.

Compounds of the general structure (I), where K! 7 H, can be obtained from compounds of the general structure (I-1). Here, you can use the methods known from the literature (CT - optionally substituted alkyl 8. (het)uarylalkyl: MLO2008/061688; Shdoshigpai oi Neiegosusiis Spetivigu 1995, 32(3), 835-839; MO2011/029808; MO2010 /020432; О52010/0152192; МО2010/101949; МО2010/043377,

Medical Sciences of the University of Geneva 2011, 2(8), 632-637; Chottai! ой Неиегосусиис Спетивигу 1977, 14(7), 1263-1265; M/O2011/020193; M/O2008/121602; M/O2006/074924; M/O2006/065794 | VI is not necessarily a substitute. alkylcarbonyl 4. (het)aryl(alkyl)ucarbonyl: ММО2010/015545; doittai oi te

Spetis! Zosieiu, ReiKip Tgtapzasiiop5 1 2002, (2), 257-274; 05 7951828 | CI is not necessarily a substitute. Alkoxycarbonyl 8 (het)aryl(alkyl/uoxycarbonyl: UMO2011/112731; MO2009/027393;

Choshtai oi Ogdapis Spetivigu 2011, 76(8), 2502-2520 | K1 is not necessarily a substitute. alkynyl: Zupipeviv 2007, (18), 2920-2923; Temanedgtop 2006, 62(16), 3856-3871; Often! oi Te Ategisap Spetisai zZosieiu 2006, 128(14), 4586-4587; Spetis! Sottipisayop5 (Cambridge, United Kingdom) 2010, 46(8), 1269-1271; MMO2009/027393 | K1 is not necessarily a substitute. alkenyl: Ogdapis Spitivig:

Ap Ipaiap Choshta! 2010, 6(1), 52-55; Eshstoreap doshigpa! oi Ogdapis Spetivshtu 2009, (1), 72-84;

MO2006/067444; MO2005/049585).

Reaction scheme 4 shows the general method of obtaining O for the synthesis of compounds (I) according to the invention.

Reaction scheme 4

AND

1 1 c

Ah in ku

A Ve-X A c

AND; TA, I -- A; TA, and

Koui cha tA Ge)

M M zo (-2) ()

The radicals A:-A»;, 0, B' and M/ have the values described above. X represents any leaving group such as, for example, chlorine, bromine or iodine. T stands for group

1 2

And H

M. Kh

M

1z where the radicals 2, 72 and 73 have the values given above, and the asterisk means the point of joining the SAMU group. 5 means the radicals described above.

Compounds of general structure (I) can be obtained from compounds of general structure (1-1).

Here, you can use the methods mentioned for the method of obtaining C.

Compounds of general formulas (11-1), (1I-1-1) and (1-2) can be used as precursors for substances of general formula (II). Substances of the general formula (11-1-14) are usually known compounds of organic chemistry that can be obtained by established methods of synthesis.

Possible ways of synthesis of cyclic aminocarboxylic acids of the general formula (11-1-1) are shown in reaction scheme 5.

Reaction scheme 5

H ve d A,

A Zh l

A, x MO,

MN A ry (9 in: her

ZE A AJ

DI! le "FOR Me

And ZhK z-vz 0 x She chn," r

HU A their A; TA, and

Ai! - (8) shi (P-1-1) about N

Y- A ke di A; A, 1 4 HER o

AK x ZAY YES 3

A, OT re and

XII - ' (ХИЙ) A: A, (Хи)

Abya (in) 2 kyu dk min o

Halogenated (heteroaromatic nitro- or amino compounds, for example, represented by the formulas (IX) and (ХМ), can be used as starting substances for obtaining aminocarboxylic acids of the general structure (11-1-1). Here, the leaving X group is replaced by a cyano group, and the latter is then subjected to acid or base hydrolysis.Halogen/cyano exchange can be accomplished, for example, by nucleophilic substitution in the aromatic ring using cyanide compounds such as, for example, sodium cyanide (05 4766219), or by a Moishgpai copper-mediated reaction oi Apiibioiis5 1994, 47(12), 1456-65.

Zo

In the case of nitro compounds (IX, X, and XII), the nitro function can subsequently be reduced to an amino function. Suitable methods for such reduction are hydrogenation and metal-mediated reactions, such as, for example, mediated by tin(II) chloride, iron powder, zinc dust and similar compounds.

Hydrogenation can be carried out in a suitable solvent in the presence of a catalyst in a hydrogen atmosphere (normal pressure or elevated pressure). Suitable for use as such catalysts are palladium catalysts such as, for example, palladium on carbon, nickel catalysts such as Raney nickel, cobalt catalysts, ruthenium catalysts, rhodium catalysts, platinum catalysts and compounds similar to them. Suitable solvents include water, alcohols such as methanol and ethanol, aromatic hydrocarbons such as benzene and toluene, open chain or cyclic ethers such as diethyl ether, dioxane and tetrahydrofuran, and esters such as ethyl acetate. Reduction reactions can be carried out in the pressure range from 1 bar to 100 bar, and the temperature can vary between -20 "C and the boiling point of the solvent used. Depending on the reaction conditions, the reaction time is between several minutes and 96 hours.

Metal-mediated reduction reactions, for example using stannous chloride, can be carried out according to the methods described in Ogdapis Zupipezev SoiY. vol. (II), 453.

In addition, (hetero)aromatic aminocarboxylic acids of the general structure (1I-1-1) can also be obtained from the corresponding methyl precursors of type (X) by oxidation.

Oxidizing agents suitable for such oxidation reactions are, for example, potassium permanganate, sodium dichromate, chromium trioxide and compounds similar to them. Viogdapis a Meadisipai SPpetivhigu Genegv 2007, 17(4), 1043-1046. It is also possible to use enzymatic methods for such oxidation reactions. PCT application, 9502061). The necessary subsequent restoration of the nitro function can be carried out similarly to the method described above.

An additional method of obtaining (hetero)aromatic aminocarboxylic acids of the general structure (1I1-1-1) is the nitration of precursors of carboxylic acids represented by formula (XI) or (XII), and subsequent recovery of the nitro function. Nitration reactions can be carried out with

With the use of methods known from the literature of Miviy5 Perid5 AppaIep deg Spetieye 1958, 611, 194-205; Ogdapikit, UMPeu-USN, 22. Edition, 358 et seq.|. The necessary subsequent restoration of the nitro function can be carried out similarly to the method described above.

In addition, (hetero)aromatic aminocarboxylic acids of the general structure (1I-1-1) can be obtained from the corresponding (hetero)daryl triflates of type (XII) using a palladium-catalyzed method (IZupipeviv 2006, (4), 594-596).

Compounds of general formula (1I-1) can be obtained from compounds of general formula (11-1-1) by established methods of synthesis. A possible path for the synthesis of cyclic aminocarboxylic acids of the general formula (1I-1) is shown in reaction scheme 6.

Reaction scheme 6

AND

MN. nm" r r

OO --- OS which A. ke

Z A, o (c); (P-1-1) (i-th)

Radicals A;:-Ah have the meanings described above. Radical K!' means the radicals described above, excluding hydrogen.

The transformation, known from the literature, of (11-1-1) into (1-1) can occur, among other things, by means of reductive amination (|Vioogdapis 85 Medisipa! Spetivigu I etsCeg5 2005, 15(21), 4752- 4756; MO2010 -142402; 052010-0324056)| or direct alkylation. dotsgtpa! oh She Ategisap SNetisa! Bosieiu 1997, 119(9), 2315-2316; Oshchoshygttai!i oi

SotrBbipayutia! Spetivigu 2006, 8(6), 834-840).

Compounds of the general formula (II-2) can be obtained from compounds of the general formula (1I-1) by established methods of synthesis. A possible path for the synthesis of cyclic aminocarboxylic acids of the general formula (II-2) is shown in reaction scheme 7.

Scheme of reaction 7 1 1 in ee

MN MN ka n kla, nshe 2 A; (c) With (P-1) (1-2)

Radicals A: Ah and E! have the meanings described above.

The conversion of compounds of the general formula (II-1) into compounds of the general formula (1-2) can be carried out similarly to the reactions known from the literature (Ш52009-0023798; УМО2009-044200;

MO2010-0853521.

Possible ways of synthesis of derivatives of heterocyclic carboxylic acids of the general formula (M) are depicted in reaction scheme 8.

Reaction scheme 8

T-Me (KHM) M o M t-NO -- 656-- t- -- t- (KHMI) on x ra (y-1) (U) t-na M (KHMII) Z 4 on (M- 2)

The radical M/ has the values described above. On! means a suitable halogen such as bromine or iodine. X represents a suitable leaving group such as, for example, chlorine. T means group 1 2

AND

M. j

M

1z where the radicals 7, 72 and 73 have the values given above, and the asterisk means the point of attachment to the groups Me, H, Nai, СОН, С(-5)ОН or С(-МЛХ.

Heterocyclic carboxylic acids of the general structure (M-1) can be obtained, among other things, from methyl derivatives of the general formula (XM) by oxidation of the methyl function. For this purpose, it is possible to use the methods already mentioned for the oxidation of methyl groups of compounds of the general structure (X).

Heterocyclic carboxylic acids of the general structure (M-1) can be obtained from the precursors of the general structure (HMI) by deprotonation using a suitable base and by capturing the corresponding carbanion with carbon dioxide MCoshigpa! oh Meaisipai!

Spetivigu 2008, 51(4), 937-947; Vioogdapis b Medisipa! Spetivigu GenNegs 2007, 17(22), 6274-6279.

Suitable bases are, for example, lithium diisopropylamide, n-butyllithium, t-butyllithium and compounds similar thereto.

Also, for the method of obtaining heterocyclic carboxylic acids of the general structure (MU-1), described above, suitably halogenated heterocycles (CHMs) are suitable. However, in this case, the carbanion is generated not by deprotonation, but by a metalation reaction

Iapdeumlapaiye Spetie, Ipiegpaiopa!i, Edition 2008, 47(2), 311-315). The best for these metalation reactions are n-butyllithium, tert-butyllithium, and isopropylmagnesium chloride.

Heterocyclic carboxylic acids of the general structure (M-1) can also be obtained from halogenated precursors of the general structure (HMI) by means of palladium-catalyzed reactions known from the literature, which leads to the corresponding heterocyclic esters of carboxylic acids (Kizviap doigpai!oi Arriiea Spetivigu 2007, 80( 4), 571-575.

Heterocyclic carboxylic acids of the general structure (M-1), in addition, can be obtained from halogenated compounds of the general structure (XMII) by the reaction of substitution of halogens with cyanides and subsequent hydrolysis of the nitrile function with a strong acid or bases (MO 20050798011.

Heterocyclic thiocarboxylic acids of the general structure (M-2) can be obtained from (M-1) similarly to the methods known from the literature, described for obtaining compounds of the general formula (PI-2).

Activated derivatives of heterocyclic carboxylic acid, such as, for example, carbonyl halides represented by the general structure (M), can be obtained by the reaction of cyclic (thiodicarboxylic acid, represented by formulas (M-1) and (y-2), with halogenating reagents, such as thionyl chloride, thionyl bromide, phosphoryl chloride, oxalyl chloride, phosphorus trichloride, etc. (Ogdapikit, UMieu-USN, 22. Edition, 496 et seq.|.

Activated carboxylic acid derivatives of the general structure (I) can be obtained using well-known methods disclosed in the literature from carboxylic acids of the formula (II-1)

Iogaapikyt, UMPeu-USN, 22. Edition, 496 et seq.; Spent Veg 1970, 788; U. At. Spent Zos 1967, 50121. Compounds of the formula (1I-1) are available for purchase or can be obtained using known methods disclosed in the literature (Zupipeviv 2006, (4), 594-596; Teigapedgop I eNeg5 1995, z6(25), 4369-72; Vioogdapis 5 Medisipa! Spetivigu I eNegv 2007, 17(4), 1043-1046; International PCT application, 9502061, Chostai oi Ogdapis Spetivigu 1954, 19, 357-64; M/O 2001083459).

Compounds of the general structure (I) are available for purchase and/or can be obtained by the following methods, which are known from the literature or analogous to them Juoigpai oi Ogdapis Spetivzigu 1990, 55(14), 4276-81; UMO 2005028429; MO 2005021485; Ogoapis I eNeg5 2010, 12(9), 1944-1947;

Temganeadtop 1999, 55(24), 7625-7644).

Compounds of the general structure (M) are usually commercially available and/or can be prepared by known methods disclosed in the literature. Spetivigu 2008, 51(4), 937-947; Vioogdapis in Medisipa! Spitivigu I eyeg5 2007, 17(22), 6274-6279; Journal of Animal Science 2007, 80(4), 571-575; MO 2005079801; doshgtai oi Ogdapis Spetivigu 2008, 73(9), 3523-3529; Vioogdapis 5 Meadisipai Spetivigu I eNegs 2005, 15(22), 4898-4906; uz2gO06069270

Compounds of the general structure (MI) can be obtained using methods known from the literature, from compounds of the general structure (II) Yuoigpa! Oi She Ategisap Spetisa! Bosieiu 2001, 123(34), 8177-8188; Ipogdapis Spitis Asia 2006, 359(6), 1912-1922.

Compounds of general structures (IX) - (CHMII) are available for purchase and/or known from the relevant specialized literature.

Oxidizing agents for the oxidation of alcohol groups are known (cf., for example, oxidizing agents in Ogdapis

Zupipeziz Bu Ohidayop m/yKp Meia! Sotrotspaz, Mi)5, De dopde, Riepit Megiad, New York, 1986;

Mapdapeze Sotroyipavz az Ohiaiigipa Adepv ip Ogdapis Spetivigu, Atai, Orep Soshp Rybiiznipa Sotrapu, and Zaie, I, 1981; TNne Ohidainyop oi Ogdapis Sotrotspa5 Bu Reptapdapaie Iop apa

NehamaYiepi Spgotiit, I ee, Orep Soshgi Rybiiepipd Sotrapu, GI and ZaiIe, Ii, 1980). Oxidation can be carried out, for example, in the presence of permanganates (for example, potassium permanganate), metal oxides (for example, manganese dioxide, chromium oxides, which are used, for example, in the form of dipyridinechromium oxide (M!) as a Collins reagent (cf. U. C SoPp5, etc.,

Teigapedgop And hey. 30, 3363-3366, 1968)). Similarly, oxidation is carried out in the presence of pyridinium chlorochromate (for example, Cory's reagent) (cf. also K. 0. Nyspipz et al., Teigapeagop

And hey. 48, 4167-4170, 1977; 0. I apaipi et al. Zupipevi5 134-136, 1979) or ruthenium tetraoxide (cf.

Z.-I. MytaNnavzni, M. Kotiua Vishpepiit -saiaiulea Ohidayop oi AIKepevz, AIsopoi5, Atipe5, Atidev, D-

And Asiatv5, Rpepoi5 apa Nuagosatfop5, in: Modegp Ohidayop Meipoa5, Vaeskmai!, dap-Egipod (Ed.), 60 UMMPeu-MSN-Mepaia StrnN 4 So. Ksal, 2004). Similarly, ultrasound-induced oxidation reactions and the use of potassium permanganate are suitable (cf. 9. Uatauchaki et al.,

Snet And hey. 3, 379-380, 1983).

All known suitable acidic or basic substances promoting the reaction can be used according to the methods described in the literature to unlock/remove the protective group ZO. When carbamate-type protecting groups are used to protect amino groups, preference is given to the use of acidic substances that facilitate the reaction. When tert-butylcarbamate protecting group (BOC group) is used, for example, mixtures of mineral acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid, or organic acids such as benzoic acid, formic acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid or toluenesulfonic acid, and a suitable diluent such as water and/or an organic solvent such as tetrahydrofuran, dioxane, dichloromethane, chloroform, ethyl acetate, ethanol or methanol. Mixtures of hydrochloric acid or acetic acid with water and/or an organic solvent such as ethyl acetate are preferred.

It is known that certain reactions and production methods can be carried out especially effectively in the presence of diluents or solvents and basic or acidic substances that promote the reaction. It is also possible to use mixtures of thinners or solvents. Thinners or solvents are preferably used in such an amount that the reaction mixture remains easily mixed throughout the process.

Suitable diluents or solvents for conducting reactions according to the invention are, in principle, all organic solvents that are inert under specific reaction conditions. Examples include: halogenated hydrocarbons (eg, chlorinated hydrocarbons such as tetrachloroethylene, tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, carbon tetrachloride, trichloroethane, trichloroethylene, pentachloroethane, difluorobenzene, 1,2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, chlorotoluene, trichlorobenzene) , alcohols (e.g. methanol, ethanol, isopropanol, butanol), ethers (e.g. ethyl propyl ether, methyl tert-butyl ether, n-butyl ether, anisole, phentol, cyclohexyl methyl ether, dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, diisoamyl ether, ethylene glycol dimethyl ether,

From tetrahydrofuran, dioxane, dichlorodiethyl ether and polyesters of ethylene oxide and/or propylene oxide), amines (for example, trimethyl-, triethyl-, tripropyl-, tributylamine, M-methylmorpholine, pyridine and tetramethylenediamine), nitrocarbons (for example, nitromethane, nitroethane, nitropropane, nitrobenzene, chloronitrobenzene, o-nitrotoluene); nitriles (eg, acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, m-chlorobenzonitrile), tetrahydrothiophene dioxide, dimethyl sulfoxide, tetramethylene sulfoxide, dipropyl sulfoxide, benzyl methyl sulfoxide, dibutyl sulfoxide, dibutyl sulfoxide, diisoamyl sulfoxide, sulfones (eg, dimethyl, diethyl, dipropyl, dibutyl, diphenyl, digexyl , methylethyl, ethylpropyl, ethylisobutyl, and pentamethylene sulfone), aliphatic, cycloaliphatic, or aromatic hydrocarbons (such as pentane, hexane, heptane, octane, nonane, and technical hydrocarbons), as well as so-called "white spirits" with components boiling in in the range from, for example, 40 C to 250 "C, cymene, oil fractions with a boiling range from 70 "C to 190 "C, cyclohexane, methylcyclohexane, petroleum ether, naphtha, octane, benzene, toluene, chlorobenzene, bromobenzene, nitrobenzene, xylene , esters (for example, methyl-, ethyl-, butyl- and isobutyl acetate, dimethyl-; dibutyl- and ethylene carbonate); amides (for example, hexamethylphosphorus-tri amide, formamide, M-methylformamide, M,M-dimethylformamide, M,M-dipropylformamide, M,M-dibutylformamide, M-methylpyrrolidine, M-methylcaprolactam, 1,3-dimethyl-3,4,5,6-tetrahydro- 2(1H)-pyrimidine, octylpyrrolidone, octylcaprolactam, 1,3-dimethyl-2-imidazolinedione, M-formylpiperidine, M,M'- diformylpiperazine) and ketones (for example, acetone, acetophenone, methyl ethyl ketone, methyl butyl ketone).

The main substances that promote the reaction, which are used to carry out the method according to the invention, can be all suitable acid-binding substances. Examples include: alkaline earth or alkali metal compounds (e.g. hydroxides, hydrides, oxides and carbonates of lithium, sodium, potassium, magnesium, calcium and barium), amidine bases or guanidine bases (e.g. 7-methyl-1,5,7- triazabicycloi|4.4.O|dec-5-ene (MTV); diazabicyclo|4.3.O|nonene (OVM), diazabicyclo|2.2.2|octane (SAVSO), 1,8-diazabicyclo/5.4.F)undecene (08 ), cyclohexyltetrabutylguanidine (CsSutvo), cyclohexyltetramethylguanidine (cSutms), M,M,M,M-tetramethyl-1,8-naphthalenediamine, pentamethylpiperidine) and amines, especially tertiary amines (for example, triethylamine, trimethylamine, tribenzylamine, triisopropylamine, tributylamine, tricyclohexylamine , triamylamine, 60 trihexylamine, M,M-dimethylaniline, M,M-dimethyltoluidine, M,M-dimethyl-p-aminopyridine, /-M-

methylpyrrolidine, M-methylpiperidine, M-methylimidazole, M-methylpyrazole, M-methylmorpholine, M-methylhexamethylenediamine, pyridine, 4-pyrrolidinepyridine, 4-dimethylaminopyridine, quinoline, a-picoline, B-picoline, isoquinoline, pyrimidine, acridine, M, M,M',M -tetramethylenediamine, M,M,M',M' - tetraethylenediamine, quinoxaline, M-propyldiisopropylamine, M-ethyldiisopropylamine, M,M'-dimethylcyclohexylamine, 2,6-lutidine, 2,4-lutidine or triethyldiamine).

Acidic substances that promote the reaction used in carrying out the method according to the invention include all mineral acids (for example, hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydroiodic acid, as well as sulfuric acid, phosphoric acid, phosphoric acid, nitric acid), Lewis acids (for example, aluminum chloride (I!), boron trifluoride or its etherate, titanium chloride (IM), stannous chloride IM)) and organic acids (for example, formic acid, acetic acid, propionic acid, malonic acid, lactic acid, oxalic acid, fumaric acid, adipic acid, stearic acid, tartaric acid, oleic acid, methanesulfonic acid, benzoic acid, benzenesulfonic acid or paratoluenesulfonic acid).

If protecting groups are indicated in the reaction schemes, all known protecting groups can be used. In particular, those described by Sgeepe T. MU., Mutsi5 R. b. MU. in Rgoiesiime sgocMmrz ip Ogdapis

Zupipeziv; doyp UMuiieu b Bopv, Ips. 1999, "Rgoiesiyop Tog She Nuagohu! agoir ipsitsaipa 1,2- apa 1,3- dioiv".

Protecting groups of the substituted methyl ether type are also suitable (for example, methoxymethyl ether (MOM), methylthiomethyl ether (MTM), (phenyldimethylsilylmethoxymethyl ether (5MOM-OV), benzyloxymethyl ether (BOM-OK), para-methoxybenzyloxymethyl ether (RMVM-OR), para -nitrobenzyloxymethyl ether, ortho-nitrobenzyloxymethyl ether (MVOM-OR), (4-methoxyphenoxy)methyl ether (p-AOM-OK), guaiacol methyl ether (ZIOM-OK), tert-butoxymethyl ether, 4-pentyloxymethyl ether (ROM-OK ), silyloxymethyl ether, 2-methoxyethoxymethyl ether (MEM-ONB), 2,2,2-richloroethoxymethyl ether, bis(2-chloroethoxy)methyl ether, 2-(trimethylsilyl)ethoxymethyl ether (ZEM-OBR), methoxymethyl ether ( MM-OV));

From the type of substituted ethyl ether (for example, 1-ethoxyethyl ether (EE-OR), 1-(2-chloroethoxy)ethyl ether (SEE-OH), 1-(2-(trimethylsilyl)ethoxy|detyl ether (ZEE-OV) , 1-methyl-1-methoxyethyl ether (MIR-ONB), 1-methyl-1-benzyloxyethyl ether (MVE-OV), 1-methyl-1-benzyloxy-2-fluoroethyl ether (MIR-OR), 1-methyl -1-phenoxyethyl ether, 2,2,2-trichloroethyl ether, 1,1-dianizyl-2,2,2--richloroethyl ether (OATE-ORM), 1,1,1,3,3,3- hexafluoro- 2-phenylisopropyl ether (NIR-OMV), 2-trimethylsilylethyl ether, 2- (benzylthio)ethyl ether, 2-(phenylselenyl)ethyl ether), ether (for example, tetrahydropyranyl ether (TNR-OV), 3-bromotetrahydropyranyl ether (3 -ViITNR-OV), tetrahydrothiopyranyl ether, 1-methoxycyclohexyl ether, 2- and 4-picolyl ether, M-oxide 3-methyl-2-picolyl ether, 2-quinolinylmethyl ether (0t-OV), 1-pyrenylmethyl ether, diphenylmethyl ether (ORM-OK), para, para'-dinitrobenzhydryl ether (OOMV-OB), 5-dibenzosuberyl ether, triphenylmethyl ether (Tg-OK), al α-naphthyldiphenylmethyl ether, para-methoxyphenyldiphenylmethyl ether (MM'TTOK), di(para-methoxyphenyl)/phenylmethyl ether (OMTTg-OK), tri(para-methoxyphenyl)phenylmethyl ether (TMTI-OB), 4-(4-bromophenacyloxy )phenyldiphenylmethyl ether, 4,44"-tris(4,5-dichlorophthalimidophenylmethyl ether (SRTI-OV), 4,44"-tris(benzoyloxyphenyl)methyl ether (TVTg-OV), 4,4-dimethoxy-3"-I (M-(MidazolylmethylUtrityl ether (IUTI-OV), 44-dimethoxy-3"-I(M-(imidazolyl-ethyl/ucarbamoyl|grityl ether (IETg-OR), 1,1-bis(4-methoxyphenyl)- 1 -pyrenyl methyl ether (Vtrt-OV), 9-anthryl ether, 9-(9-phenyl)xanthenyl ether (Rihui!-

ОВ), 9-(9-phenyl-10-oxo)anthryl (tritylon ether), 4-methoxytetrahydropyranyl ether (MTNR-OV), 4-methoxytetrahydrothiopyranyl ether, 5,5-dioxide A- methoxytetrahydrothiopyranyl, 1-(2-chloro -4-methyl)phenyl|-4-methoxypiperidin-4-yl ether (STMR-OV), 1-(2-fluorophenyl)-4-methoxypiperidin-4-yl ether (Gtr-OV), 1,4-dioxan- 2-yl ether, tetrahydrofuranyl ether, tetrahydrothiofuranyl ether, 2,3,3a,4,5,6,7,7a-octahydro-7,8,8-trimethyl-4,7-methanebenzofuran-2-yl ether (MVE- OK), tert-butyl ether, allyl ether, propargyl ether, para-chlorophenyl ether, para-methoxyphenyl ether, para-nitrophenyl ether, para-2,4-dinitrophenyl ether (OMR-OV), 2,3,5,6 -tetrafluoro-4-(trifluoromethyl)phenyl ether, benzyl ether (Bp-OR)); type of substituted benzyl ether (for example, para-methoxybenzyl ether (MRM-OV), 3,4-dimethoxybenzyl ether (OMRM-OK), ortho-nitrobenzyl ether, para-nitrobenzyl 60 ether, para-halobenzyl ether, 2,6-dichlorobenzyl ether, para-aminoacylbenzyl ether (RAV-OK), para-azidobenzyl ether (А?Б5-ОНВ), 4-azido-3-chlorobenzyl ether, 2-trifluoromethylbenzyl ether, para-(methylsulfinyl)/benzyl ether (М5іб-ОВ )); type of silyl ether (for example, trimethylsilyl ether (TM5-OK), triethylsilyl ether (TE5-OK), triisopropylsilyl ether (TIRBZ-OK), dimethylisopropylsilyl ether (IROM5-OK), diethylisopropylsilyl ether (OBIRZ-OK), dimethylhexylsilyl ether (ТО5 -

OK), tert-butyldimethylsilyl ether (TVOM5-OK), tert-butyldiphenylsilyl ether (TVORB-OK), tribenzylsilyl ether, tri-para-xylylsilyl ether, triphenylsilyl ether (TRZ-OK), diphenylmethylsilyl ether (ORM5-OK), di -tert-butylmethylsilyl ether (OTVM5-OK), tris(trimethylsilyl)silyl ether (sisyl ether), di-tert-butylmethylsilyl ether (OTVM5-OK), tris(trimethylsilyl)silyl ether (sisyl ether), (g-hydroxystyryl) udimethylsilyl ether (H5YUM5-OV), (2-hydroxystyryl)diisopropylsilyl ether (NBOI5-OK), tert-butylmethoxyphenylsilyl ether (TVMRB-OK), tert-butoxydiphenylsilyl ether (ORTVO5-OV)); of the ester type (for example, esters such as formate, benzoyl formate, acetate (Ac-OK), chloroacetate, dichloroacetate, trichloroacetate, trifluoroacetate (TEA-OK), methoxyacetate, triphenylmethoxyacetate, phenoxyacetate, para-chlorophenoxyacetate, phenylacetate, diphenylacetate (ORA -OK), nicotinate, 3-phenylpropionate, 4-pentoate, 4-oxopentoate (levulinate) (Hem-OMV) 4,4-(ethylenedithio)pentanoate (Hem5-OB), 5-I3-bis(4-methoxyphenyl)hydroxymethoxyphenoxy levulinate, pivaloate (Rkhm-OV), 1-adamantanoate, crotonate, 4-methoxycrotonate, benzoate (B2-OK), para-phenylbenzoate, 2,4,6-trimethylbenzoate (mesitoate), 4-(methylthiomethoxy)butyrate (MTMV -OB), 2-(methylthiomethoxymethyl)benzoate (MTMT-OB), of the ester type (for example, methyl carbonate, methoxymethylcarbonate, 9-fluorenylmethylcarbonate (Etos-OK), ethyl carbonate, 2,2,2-trichloroethyl carbonate (Thos-OB), 1,1-dimethyl-2,2,2-trichloroethyl carbonate (TSVOS-ORV), 2-(trimethylsilyl)ethyl carbonate (ТМ5-ОВ), 2-(phenylsulfonyl)ethyl carbonate (Р5-ОНВ), 2-(triphenylphosphonio)ethyl carbonate ( Rheos-OK) , tert-butyl carbonate (Voc-OK), isobutyl carbonate, vinyl carbonate, allyl carbonate (AIPos-OK), para-nitrophenyl carbonate, benzyl carbonate (27-OK), para-methoxybenzyl carbonate, 3,4-dimethoxybenzyl carbonate, ortho-nitrobenzyl carbonate, para-nitrobenzyl carbonate, 2- dansylethyl carbonate (Opseos-ONB), 2-(4-nitrophenyl) ethyl carbonate (Mreos-OB), 2-(2,4-

Zo dinitrophenyl)ethyl carbonate (Opreos)), and of the sulfate type (for example, allyl sulfonate (AI5-OK), methanesulfonate (M5-OB), benzyl sulfonate, tosylate (T5-OH), 2-(4-nitrophenyl)ethyl|sulfonate (Mre5 -OV)).

Suitable catalysts for carrying out catalytic hydrogenation in the method according to the invention are all conventional hydrogenation catalysts, such as, for example, platinum catalysts (e.g. platinum plate, platinum sponge, platinum black, colloidal platinum, platinum oxide, platinum wire), palladium catalysts (e.g. , palladium sponge, palladium black, palladium oxide, palladium on carbon, palladium colloid, palladium on barium sulfate, palladium on barium carbonate, palladium hydroxide), nickel catalysts (eg, reduced nickel, nickel oxide, Raney nickel), ruthenium catalysts, cobalt catalysts (e.g. reduced cobalt, Raney cobalt), copper catalysts (e.g. reduced copper, copper

Raney, Ullmann's copper). Preference is given to the use of catalysts based on noble metals (for example, platinum and palladium or ruthenium catalysts), which can be deposited on a suitable substrate (for example, coal or silicon), rhodium catalysts (for example, tris(triphenylphosphine)rhodium(I) chloride in the presence triphenylphosphine). In addition, it is possible to use "chiral hydrogenation catalysts" (for example, catalysts containing chiral diphosphine ligands such as (25,35)-(-)-2,3-bisidiphenylphosphino)butane ((5,5)-chiraphos or ( K)-(-)-2,2- or (5)-(-)-2,2'-bisidiphenylphosphino)-1,1-binaphthalene (K(--VIMAR or 5(-)-

VIMARI), with the help of which the proportion of a single isomer in a mixture of isomers increases, or the formation of the second isomer is almost completely suppressed.

Salts of compounds according to the invention are obtained by standard methods. Typical acid addition salts are, for example, salts formed by reaction with inorganic acids, such as, for example, sulfuric acid, hydrochloric acid, hydrobromic acid, phosphoric acid, or organic carboxylic acids, such as acetic acid, trifluoroacetic acid, citric acid, succinic acid, butyric acid, lactic acid, formic acid, fumaric acid, maleic acid, malonic acid, camphoric acid, oxalic acid, phthalic acid, propionic acid, glycolic acid, glutaric acid, stearic acid, salicylic acid, sorbic acid, tartaric acid, cinnamic acid, valeric acid, picric acid, benzoic acid, or organic sulfonic acids such as methanesulfonic acid and 4-toluenesulfonic acid. 60 Also typical are salts of compounds according to the invention, formed from organic bases, such as

For example, pyridine or triethylamine, or salts formed from inorganic bases, such as, for example, hydrides, hydroxides or carbonates of sodium, lithium, calcium, magnesium or barium, provided that the compounds of the general formula (I) have a structural element suitable for the formation of such a salt.

Synthesis methods for obtaining heterocyclic M-oxides and t-amines are known. They can be obtained using peroxyacids (for example, peracetic acid and metachloroperbenzoic acid (MCPA), hydrogen peroxide), alkyl hydroperoxides (for example, tert-butyl hydroperoxide), sodium perborate and dioxiranes (for example, dimethyldioxirane). These methods were described, for example, by T. GG. SiYspgibi, in Sotrgepepvzim Ogdapis zupipeviv, vol. 7, ss. 748-750, 1992, 5. M. Ieu, (ed.), Regdatop Rgez5; M. Tivieg, V. Fapompik, in Sotrgepepvzime Neiegosusiis

Spetizvigu, vol. 3, pp. 18-20, 1984, A. 7. Voshop, A. MeoKiPor, (Ed.), Regdatop Rgez5; M. K. Sgitteii,

V. K. T. Keeepe in Admapsez ip Neiegosusiis Spetivigu, vol. 43, pp. 149-163, 1988, A.K. Kaigy2kKu, (ed.),

Asadetis Rge55; M. TivzIeg, V. Mapoupik, in Admapsez ip Neijegosusiis Spetivigu, vol. 9, pp. 285-291, 1968, A. K. Kaigygkku, A. U. Voshop (Eds.), Asadetis Rge55; 5. MU. N. Speezetap, E. 5. sch. MegwiiIK in Admapsez ip Neiegosusiis Spetivigu, vol. 22, ss. 390-392, 1978, A. K. Kaighiku, A. U. Voshop, (eds.),

Asadetis Rhev5.

Experimental part

Method of obtaining A

Example OP) 4-Bromo-M-(4-chloro-3-(1-cyanocyclopropyl)/ucarbamoyl|phenyl)-3-(1-fluorocyclopropyl)-1-methyl-1H-pyrazole-5-carboxamide

IS

120 mg (0.45 mmol) of 4-bromo-3-(1-fluorocyclopropyl)-1-methyl-1H-pyrazole-5-carboxylic acid is suspended in 20 ml of dichloromethane n.a., and add 0.02 ml of M,M-dimethylformamide c.d.a. 0.119 ml (1.36 mmol) of oxalyl chloride was added dropwise to this mixture. The mixture is then stirred at room temperature for 30 minutes and then under reflux for 30 minutes. After cooling, the reaction mixture is concentrated under reduced pressure on a rotary evaporator. The raw product obtained in this way is introduced into the further reaction

Ko) without additional cleaning. 108 mg (0.45 mmol) of 5-amino-2-chloro-M-(1-cyanocyclopropyl)benzamide and 92 mg (0.68 mmol) of silver(I) cyanide are first placed in 10 ml of dichloromethane n.a. A solution of 129 mg (0.45 mmol) of 4-bromo-3-(1-fluorocyclopropyl)-1-methyl-1H-pyrazole-5-carbonyl chloride in 10 ml of dichloromethane n.a. is added dropwise to this suspension. The reaction mixture was stirred at room temperature for 16 h, and then filtered through silica gel, and the precipitate on the filter was washed with ethyl acetate. Solvents are removed under reduced pressure on a rotary evaporator.

This gives 170 mg (7895) of 4-bromo-N-(4-chloro-3-(1-cyanocyclopropyl)ucarbamoyl|phenyl)-3-(1-fluorocyclopropyl)-1-methyl-1H-pyrazole-5-carboxamide in the form of a colorless solid. "H-NMR (400 MHz, dve-DMSO): b - 10.96 (5, 1H), 9.49 (5, 1H), 7.85 (a, 1H), 7.74 (ai, 1H), 7.55 (a, 1H), 3.93 (5, ZN), 1.57-1.61 (t, 2H), 1.40-1.45 (t, 2H), 1.23-1.28 (t, 2H), 1.08-1.11 (t, 2H) ppm

VERH-MS2): IodR - 2.50, mass (etc/2) - 482 MANI".

Method of obtaining V

Example (2) M-(4-Chloro-3-(1-cyanocyclopropyl)/ucarbamoyl|phenyl)-M,1-dimethyl-3,4-bis(trifluoromethyl)-1H-pyrazole-5-carboxamide

EE EC

E E M

IS

Uk o ZA

M

M sn, /

But (fr

150.0 mg (0.29 mmol) of 2-chloro-5-(methyl(C1-methyl-3,4-bis(trifluoromethyl)-1H-pyrazol-5-yl|carbonyl)iamino)benzoic acid is suspended in 5.0 ml of dichloromethane ch.d. .and. Then, 0.02 ml of M,M-dimethylformamide n.d.a. is successively added to the suspension. and 0.075 ml (0.86 mmol) of oxalyl chloride. The reaction mixture was stirred at room temperature for 0.5 h. and then heated under reflux for 40 minutes. The solvent is removed under reduced pressure on a rotary evaporator. The formed 2-chloro-5-(methyl(/1-methyl-3,4-bis(trifluoromethyl)-1H-pyrazol-5-ylcarbonyl)iamino)benzoyl chloride is used for the next stage of synthesis without additional purification. 68.3 mg (0.58 mmol) of 1-aminocyclopropanecarbonitrile hydrochloride is first placed in 5.0 ml of dichloromethane n.o.s., and then 0.148 ml (0.86 mmol) of M-ethyldiisopropylamine and 156 mg of 2-chloro-5-(methyl/ (1-methyl-3,4-bistrifluoromethyl)-1H-pyrazol-5-yl|carbonyl)amino)benzoyl chloride (0.29 mmol) dissolved in 5.0 ml of dichloromethane n.a.

The reaction mixture was stirred at room temperature for 16 hours. The reaction solution is diluted with 30 ml of ethyl acetate. The organic phase is washed twice with 1 n. hydrochloric acid, once 1 n. with an aqueous solution of sodium hydroxide and once with a saturated solution of sodium chloride. The organic phase is dried over magnesium sulfate and filtered, and the solvent is removed on a rotary evaporator under reduced pressure.

The crude product is purified by preparative HPLC. This gives 64 mg (4595) of M-(4-chloro-3-(1-cyanocyclopropyl)/ucarbamoyl|phenyl)-M,1-dimethyl-3,4-bistrifluoromethyl)-1H-pyrazole-5-carboxamide as colorless solid. "H-NMR (400 MHz, az-acetonitrile, mixture of amides in cis- and trans-configurations): b - 7.42-7.66 (t, 2H), 7.40 (y, 1H), 7.29 (a, 2H), 7.18 ( yes, 1H), 3.83 8. 3.99 (2 5, together ЗН), 3.46 8. 3.23 (2 5, together ЗН), 1.54-1.60 (t, 2Н), 1.25-1.37 (t, 2Н) m.d.

VERH-MS2): IodR - 2.81, mass (it/z) - 494 MANI".

The method of obtaining S

Example (50). M-14-Chloro-3-(1-cyanocyclopropyl)carbamoyl|phenyl)-M-ethyl-3-(pentafluoroethyl)-1-propyl-4-trifluoromethyl)-1H-pyrazole-5-carboxamide

EE Mo

EMMA ke U

E g NM c) pis 7 o (FI sn,

Koo) 70 mg (0.13 mmol) M-(4-chloro-3-(1-cyanocyclopropyl)carbamoyl|phenyl)-3-(pentafluoroethyl)-1-propyl-4--'trifluoromethyl)-1H-pyrazole-5- carboxamide and 35 mg (0.14 mmol) of potassium carbonate are suspended in 1.4 ml of M,M-dimethylformamide n.d.a. During 16 hours a total of 29 mg (0.19 mmol) of iodethane is added little by little to the mixture. After the addition is complete, the reaction solution is stirred at room temperature for 20 hours. The reaction mixture is diluted with water, and the aqueous phase is extracted three times with ethyl acetate. The combined organic phases are washed twice with saturated sodium chloride solution, dried over sodium sulfate and filtered. Solvents are removed on a rotary evaporator under reduced pressure.

The crude product is purified by column chromatography on silica gel. This gives 30

MG (4195) M-(4-chloro-3-(1-cyanocyclopropyl)carbamoyl|Ifenyl)-M-ethyl-3-(pentafluoroethyl)-1-propyl-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide in the form of a colorless solid. "H-NMR (400 MHz, d6-DMSO, a mixture of amides in cis- and trans-configurations): b - 9.56 8. 9.42 (25, together 1H), 7.69 8. 7.56 (20, together 1H), 7.63 8. 7.42 (29, together with 1H), 7.48 85. 7.28 (24d0, together with 1H), 3.52-4.32 (t, 4H), 0.79-1.87 (t, 12H) m.d.

VERH-MS 2): IsdR - 4.06, mass (t/7) - 586 MANI.

Method of obtaining Yu

Example (40) M-3-(Acetyl(1-cyanocyclopropyl)carbamoyl|-4-chlorophenyl)-1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide

E E SM

ME ee r u"

E E M

E 6)

H |c) / i zho o SI 300 mgo (0.57 mmol) /M-(4-chloro-3-(1-cyanocyclopropyl)ucarbamoyl|phenyl)-1-methyl-3-(pentafluoroethyl)-4-"(trifluoromethyl )-1H-pyrazole-5-carboxamide is dissolved in 6.0 ml of dichloromethane n.d.a. and cooled in an ice bath. 0.17 ml (0.99 mmol) of M-ethyldiisopropylamine and 49 mg (0.62 mmol) of acetyl chloride are successively added to the solution. The reaction mixture is then heated to room temperature and stirred for 16 h. The reaction solution is diluted with dichloromethane and then washed with water. The organic phase is dried over sodium sulfate and filtered, and the solvent is removed on a rotary evaporator under reduced pressure.

The crude product is purified by preparative HPLC. This gives 130 mg (40905). M-(3-

Acetyl(1-cyanocyclopropyl)carbamoyl|-4-chlorophenyl)-1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide as a colorless solid. "H-NMR (400 MHz, dve-DMSO): b - 11.49 (5, 1H), 7.90 (a, 1), 7.70 (da, 1nH), 7.57 (a, 1H), 4.03 (5,

ZN), 2.49 (5, ZN), 1.85-1.91 (t, 2H), 1.57-1.67 (t, 2H) ppm.

HPLC-MS): IsdR - 3.81, Mass (t/2) - 572 (MANI. a) Note regarding the determination of IsdR values and mass detection: Determination of the given values of IsdR. was carried out in accordance with the EEC directive 79/831 Appeh M.A8 using HPLC (high-performance liquid chromatography) on a reversed-phase column (C18). RH system

Adpyepi 1100; 504.6 7ogra Esiirhe Riy5 C18 1.8 micron; mobile phase A: acetonitrile (0.195 formic acid); mobile phase B: water (0.099565 formic acid); linear gradient from 1090 acetonitrile to 9595 acetonitrile for 4.25 min, then 9595 acetonitrile for a further 1.25 min; oven temperature 55 °C; flow rate: 2.0 ml/min. Mass detection was performed using the Addiepa M50O system.

b) Note regarding the determination of IdR values and mass detection: The indicated IdR values were determined in accordance with the EEC directive 79/831 Appech M.A8b by means of HPLC (high-performance liquid chromatography) using a reversed-phase column (C18).

NRI100; 5074.6 7ogtbach Esiirze Riy5 C18 1.8 micron; mobile phase A: acetonitrile (0.195 formic acid); mobile phase B: water (0.08 95 formic acid); linear gradient from 5 90 acetonitrile to 9595 acetonitrile for 1.70 min, then 95 95 acetonitrile for a further 1.00 min; oven temperature 55 "C; flow rate: 2.0 ml/min. Mass detection was performed using a mass detector Misgotav55 2092000 from UMategv.

The compounds listed in Tables 1 4. 2 were prepared using the preparation methods

A - 0, described above.

Table 1 1 2 (in / m, more

A. | M

TA rya

Example Mass

Me kh 7 y V ATI A ASIA A M It/21 y 1 1- 1-cyanocyclo- | 2.50 1 |fluorocyclo| Ve Me N snisnissi| sn H pvvot t 482 propyl propyl ev i | the same | 60 1eeee|eio1 I Tvevev og

Table 1 1 2 (9)

CC;

UM M from XX m

And K

Az

M raya ke (well

Mass of 1 1-1-cyanocyclo- | 2.46

Z )khporcyklo si Me Me snu sn | ss sn n still opyl 24662 propyl p pentaph- 1-cyanocyclo- | 3.77 a) 4 torethyl SEZ Me Me sSnNISNISSII SN KI KE propyl a 1972 pentaph- 1-cyanocyclo- | 3.59 a) toretil SE» Me Me sNISsNI|ССИ| CH o Me propyl a) 1998 pentaph-1-cyanocyclo- | 3.36 a) ovo denta SEZ Me KE snISSsNI|ССИ| SN KI Nn propyl a) 1958 topom | se | me | but fsnfsnfiso|sni o! but | vn torethyl butyl pentaph-1-cyanocyclo- | 3.21 a) ovo denta SE" Me Me sSnNISNISSII SN KI NN propyl au 1944 1-cyanocyclo- CH o Hn propyl a) 480 pentaph-1-cyanocyclo- | 3.27 a) toretil SEZ Me Нн сниСсНИ|ССИ| SN KI Nn propyl au 1930 se zhk eevosv|enoo| but euro in propyl 1-cyanocyclo- 1 zhk eearsv|enoo| but euro pentaph-1-cyanocyclo- with ek ||| ko (ev vo pentaph- 1-cyanocyclo- z se | z | 0 en|enosv|enos| no cher vot v, 5 oloremy | С | me | no |snfsnfso|sni o | proponp| rodi vyt vve toretyl propyl pentaph- 1-Cyanocyclo- ee | eeaos|enno|no (ovryaeu 1- - 17 I|fluorocyclo) SI Me n snu sn | ss sn n 1 Cyanocyclo: 2.50| 436 propyl p pentaph- 1-cyanocyclo- zi | b 1 yaen |vnrskoso| he o) zhet eeveko pentaph- methoxy- 1-cyanocyclo- vi se | the same | oek en|snyso|snyo| n | chernn vv yav.

Wednesday, en|enivo|enio| new eovny rev p torethyl carbonyl propyl pentaph- methoxy- methoxy- |1-cyanocyclo- 21 lorem | se | Me | saroshi |SN|Sn|so|sni about | roonii | prot (ee2| wav pentaph- ethoxy- ethoxy- | 1-cyanocyclo- 22 rmy | С» | Me | frbony (СН СН со сн) ОЙ orbonia | propl60, 67a 2,2- - pentaph-' 1-cyanocyclo- zbo my own -2-yn-1- 1-cyanocyclo-ee is introduced into enovo|enoo| no ov ve pentaph- 1-cyanocyclo- she | z | een|e|enuo1 ko (von ve i pentaph- 4- 1- cyanocyclo- se Goremy | se | Me | lorosyunl sn|sn|so|sn i o| no | rod no) vva

Table 1 1 2 vet Mch and. m

A. M «y ve (1) wheatgrass ee | eko snosnosa nosno vet av vo

Se fshey | its | jo nt vnoon|eaenisi| noru te, shoi ev | veins |enenrvatenooi reve vo from the body | dream me en en|enosa vnoi vu rv in zosh | his goal |enenosya vnoi duet vve ish with in enen|eatenosi no era ve zsheoi in | I|nenenvatenooi 0 dav janv) she en 0100 enreniyaeivnooi 0 vu rlvn she en 8010 enreniyaeivnooi 0 duet vv ish sv | ee enoon|eauenosi no eru zosh ov || in eevva tenisi 0 data vv) she sk enrenosa ono penya Gdvsche re ot she s 81 zh |enrenssya vnoi same still vpe ele others same 100 1enoon|eaenioi noru, yav she sv | | in ee varnooi 0 ancient vv) ee | his menu is enenosya vnoi 0 desherav nn av orem |sulfny| Me | NN |snfsnfso|sn o! n ro net) won yav oretmy | That's it R Me snosnososo sno) me rode 26, vav ato loremy | St | R | me snfsnf|skfsn o) me | "rodya nov) tu zv loremy | S | ve | Me |snfsn|sk|sn o) me | "ro alv) vve 39 ory Ts|suefony| Me | NN |snfsnfso|sn o! n ro vat) vo vo varieties | That's it RO in snosnososo sno) no rody ov, vv) 5oloremy | with | R vo fsnfsnfso|sn io) v rod nevi vla ve loremy | C | | in f|snfsnfso|sn o) in | kind of war war ve orem | That's it Me | aty (sn snoso sn! o) no rodi 363 572 el | echo1e (Sho ereyuryuyusnoo ko Gete i 2 ee ee nieresi k Tetriare -en-1-il di

Table 1 1 2 (9)

CC;

UM M from XX m. in DM m

Az

M raya ve (i-i)

Mass and 1 pentaph-pyridine-4-1-cyanocyclo- lorem | That's it Me | to pour |snfsnfso|sn o) n | ro neo) here is pentaph-prop-2-1-cyanocyclo-57 ory | Se cha) MO snosnososo sn io) no rodi vv, vva pentaph-prop-2-1-cyanocyclove lorems | Se |c) M |snfsnfss|sn o) n | swarm ze5| vve ve loremy | C | Me | n |snfskfswisni o! n | roya avvi og torethyl propyl pentaph-1-cyanocyclo- ovo lorem | That's it Me | proysny |snfsn|so| sleep about | offer genus nev pentaph-1-cyanocyclo-vorm | Se 0 me | but snosnososo sno) in genus 366, vvv pentaph-1-cyanocyclo-v2 lorems | That's it Me | n |snfsnfss|sn o) me | kind zve) you ve loremy | That's it Me arovl |sn|snfso|sn o! but | roya av| vt torethyl carbonyl propyl pentaph-2 1-cyanocyclo- 64 Igoretyl CEz | trifluor n sni sno ssi| sn H propyl 360) 598 ethyl 1-cyanocyclo- all | St | me | but |snfsnfiso|sni 8) n pentaph-1-cyanocyclo-ee varieties | That's it Me | Me tolerable sleep! 8) pits of pentaph-1-cyanocyclo-67 lorem | That's it me | n |snfsn|ss|sn 8| n | would be loremy | C | me | in |snfsnfso|sn 8) n | p torethyl propyl pentaph-1-cyanocyclo- lorem | That's it me | Me |snfsnfso|sni 8) me | p pentaph-1-cyanocyclo-oto rmy | That's it Me | Me snosnoso sn! 8) you 1- . supports some | me |snfsniso sno no - propyl propyl 1-cyanocyclo- t 1svo| St me | me |snfsn|ss|sni in! n r and toret| se | me | but |snfsnfso|sn 8) n torethyl propyl 1- . otzoieiny vme | but |onphonosnoe but - propyl propyl 1-cyanocyclo-zisv | St | me | nn |snfsv)svisni 8)! n 1-cyanocyclo-sv | se) me | but the ssnososvsn iv. holes of pentaph-1-cyanocyclo-ololorum | St | me | but |snfsv)so|sn c) n two lorems | with | me | n |snfsnfswisni 8) n torethyl propyl pentaph-1-cyanocyclo-79 lorem | with | me | n |snfsnfso|sni in | offers| ro pentaph-1-cyanocyclo-orem | se | me | n |sn|sa|sv|sni8| N

Table 1 1 2

M M i, m

A. mu yo ved) pi rik i y

Me and izhe a || neni dreams well propyl ov2 |(oreti | si | Me | vcetl |sn|snfsa|sn) 5 acets rodi ovo |(oreti | s | Me | roni |SN|snfsa|sn| 5) nya ov forms | That's it Me | orboni |СН|сн со|сн| 8) mn | "ro

I thought about the era. nyszhnysyai YASINYA ZaNYNY of se) zh lyu enisnivo sniv propanoil ve (ory | si | me | on |snfsme|sa sn) 5) ny ve yuoremy | here me | n Ts|snisn sC|sn|8) n |" ovo (ory | s | me |bbd" |snfsnfsa|sn| 8) nd in (orets | se | me | no |snfisnfsye)sn|) 5) no ov2 |(orets | S | Me lorbonii|sn|snfsa sn 8) no dya oez |Muremy | C | Me vobushvy|snisn so|sn| 5). C | Me | prolons |sn|sn so|sn| 5) n |" ee (orty | s | | no |snfsnfsa|sn| 8) nd ve (ory | s | R | no |snfsnfsa|sn| 8) no ooo (orets | se | R | no |snfsnfsye) sn|) 8) but tot forms | s | | n Ts|snisnisye|sn|5) n |" oto (rest | s | | me |snfsn|sa|sn| 8) nd loz (oreti | se | me | in |snfsvusa|sn| 5) but otoe(oreti | s | me | no |snfsnfsa|sn) 5 ) of Morema's uncle | C | in | me Tsn|sniso|sn|5) me | "ro

Standing (the eagle of Sulfans! Me | M |snfsnfsa|sn|8| n

Table 1 1 2 (9)

CC;

UM M from XX m

A. Shshsh m

Az

M raya ve (i-i)

Prikl Mass o x 72 7 V' A I| Ag AZI A | M It/yai and 1 pentaph-1-cyanocyclo-o7oloremy | se | in | in fsnfsnfso|sn 8) but pentaph- - 1-cyanocyclolov ory | С 0 Me cenometi sn demolition sn | 8) pentaph-methyl-1-cyanocyclo-ated pores |sulfny| Me | NN |snfsnfss|sni 8! n oo lorems | C | R | Me snfsnfso|sni 8) me | ro torethyl propyl pentaph-1-cyanocyclo-otolorem | with | R | me Zsnfsnfsk)sni 8) me | p pentaph-1-cyanocyclo-omhoyurmy | That's it c) Me snisnosye sn) 8) but i pentaph-methyl-1-cyanocyclo-ozlorem sufone| Me | NN |snfsnfss|sni 8) n me oloryum | with | R | in fsnfsnfso|sn 8) but torethyl propyl pentaph-1-cyanocyclome oloremy | with | R | in fsnfsnfso|sn 8) in r pentaph-1-cyanocyclo-omeormy | That's it |in osnosnoso sn! 8) and pentaph-1-cyanocyclo-omtolorems | C | Me | vet |snfsnfss|sn 8! n r pentaph-pyridine-3-1-cyanocyclome lorem | That's it me | pour |snfsnfso|sni 8! n 2- - pentaph-1-cyanocyclo- ziv | 2-en-1-yl pentaph-pyridin-4-1-cyanocyclo-oo lorem | That's it me | pour |snfsnfso|sn 8! n r pentaph-prop-2-1-cyanocyclo-opor | С cha) BUT tolerable sn | 8) pits of pentaph-prop-2-1-cyanocyclolag lorema | С |c) BUT snfsnfiss|sn 8) n | Roz Lorem | C | me | but |snfsefswisni 8) n torethyl propyl pentaph-1-cyanocyclo- opelorem | That's it Me | proyons |sn|sn|so|sni in | offer ro pentaph-1-cyanocyclo- supports | C9 0 Me | but osnosnoso sn |c) vo i pentaph-1-cyanocyclopav lorem | That's it me | but |snfsnfss|sn c) me | ro ot oloremy | se | Me role |sn|snfso|sn 8! n torethyl carbonyl propyl pentaph- 2 1-cyanocyclo- 128 torethyl CE» trifluoro Hn snISNSCI|SNI 5 Hn propyl ethyl

Table 2 1 2

AND

M Kk from ra

MA

AND

Az va (IB)

Mass

Example 1 2 Z 1 1 2 Z 4 a pe 7 7 7 v A A A A M (tya 1 1- 1- 129 | fluorocyclo- Vg Me H cSniISNISSI| sn H cyanocyclo- propyl propyl 1-

SEZ SE» Me Me snisSsNn/I|SSII| сн Нн cyanocyclopropyl 1-1-131 | chlorcyclo- SI Me Me sSniISNISSI| sn H cyanocyclo-propyl propyl 1- pentaph- - propyl 1- pentaph- - propyl 1- pentaph- - propyl 1- torethyl butyl 1- pentaph- - propyl 1- ie |c) me | nosnfsnososno o no Menoshki" propyl 1- pentaph- - propyl 1- zoisv o | svo) me | nosnfsa svisnoo 0 but inoshki" propyl 1- 140 SEZ SE" Me NN sniISSI| СВИ сн Нн cyanocyclo-propyl 1- pentaph- - propyl 1- pentaph- - propyl 1- pentaph- - propyl 1- pentaph- - propyl

Table 2 1 2

AND

M Kk from ra

MA

AND". | M

Az va (IB)

Mass

App. 7: 7 V d'| Ah | dz | where | Ma. Me It/2 1 1- 1- 145 | fluorocyclo- SI Me H cSniISNISSI| sn H cyanocyclopropyl propyl 1- torethyl and propyl 1- pentaph- methoxy- - propyl 1- pentaph- ethoxy- - propyl 1- pentaph- methoxy- methoxy- | . propyl 1- pentaph- ethoxy- ethoxy- | . propyl 2,2- 1. pentaph- dimethyl- - 151 torethyl CE» Me of propane snisСсНн/I|ССІІ| сн Нн cyanocyclo- p propyl 1- pentaph- - propyl 1- pentaph- - propyl - 1- pentaph- prop-2-yn- - Y propyl 1- pentaph- - propyl pentaph- schi 1- 156 SE» Me chlorbenzI| SN | SN | SSI | СН Нн cyanocyclo- torethyl and yl propyl - 1- pentaph- isobutyrs - 157 torethyl CE» Me p snisSsНn/I|ССІІ| сн Нн cyanocyclopropyl yiv) lentaph- | se Me |buggini| sleep sleep ss | sn H ivnocyclotorethyl C 1-yl cyanocy! propyl 1- pentaph- - propyl - 1- pentaph- pyridine- - And propyl

Table 2 1 2

AND

-e M Kk from ry

MA

AND". | MIND

Az va (IB)

Mass

App. 22 7: In AT Ag | yes | A m a . Me It/2 1 1- 161 pentaph, SEz Me snisSsNn/I|SSII| сн Нн cyanocyclo-r propyl 1-162 pentaph, SEZ shchi n sni sn | ss sn No | cyanocyclo- r propyl 1- 163 pentaph, SEZ Re n sni sn | ss sn No | cyanocyclo- r propyl 1- 164 pentaph, SEz Rg n sni sn | SE | sn No Icyanocyclo-r propyl 1- 165 pentaph, SEZ shchi n sni sn | se | sn No |cyanocyclo- r propyl 1- 166 pentaph, SEz KE Me snisSsNn/I|ССІІ| sn Hn cyanocyclo-r propyl 1-167 pentaph, SEZ Me EE sn | svg | ss | сн Но |cyanocyclo-r propyl 1-168 pentaph, SE» Me Нн снисСсНн/И|ССІИ| sn acetyl |cyanocyclo- r propyl 1- 169 pentaph, SEz KE Me snisSsNn/I|ССІІ| sn Me |Icyanocyclo- r propyl pentaph- | Methyl". 1. 170 torethyl sulfani Me Hn snisSsNn/I|ССІІ| сн Нн cyanocyclo-r propyl-1-pentaph-cyanomet. propyl pentaph- | Methyl 1-173 torethyl sulfini Me Hn snisSsHn/I|ССІІ| sn Hn cyanocyclo-r l propyl 1- 174 pentaph" SEZ Re Me sn | ss sn Me Icyanocyclo- r propyl 1- pentaph- - propyl 1- pentaph- - propyl

Table 2 1 2

AND

M Kk from the river

MA

AND". | M

Az

M

- "what! (IB)

Mass

App. 22 7: In AT Ag | yes | A m a . Me It/2 1 pentaph-methyl | 1- 177 toretype sulfony Me Hn snisSsHn/I|ССІІ| сн Нн cyanocyclo-рl propyl 1-178 pentaph, СЕз Рг Е сни сн | ss sn No Icyanocyclo-r propyl 1-179 pentaph, SEz Рg E sni sn | ss sn Eyi o |cyanocyclo-r propyl 1- 180 pentaph, SEz KE KE snisSsNn/I|ССІІ| sn KE cyanocyclo-r propyl 1-181 pentaph, CE» Me acetyl | CH) CH | SS | СН Нн cyanocyclo- p propyl - 1- pentaph- pyridine- - Y 2- 1- 183 pentaph, SEz Me full snisSsn/|СсСсІІ| сн Нн cyanocyclo- p - propyl yl - 1- pentaph- pyridine- - Y iv5 | lentaf- | sr, |propain)Y about |snisn/ssi| sn H cyanocyclotorethyl C 1-yl and propyl ivb | pentaph- | or, | prop-g- H sn | sleep ss | sn H cyanocyclotorethyl Zen-1-yl and propyl 1-187 pentaph, SEZ Me n CH | se | svi | CH No |cyanocyclo-r propyl 1-188 pentaph, SEz Me snisSsNn/I|ССІІ| sn cyanocyclo-r propyl 1-189 pentaph, SEz Me Hn snisSsNn/I|ССІІ| sn KE cyanocyclo-r propyl 1-190 pentaph, SEz Me Нn snisSsНn/I|ССІІ| sn Me |Icyanocyclo-r propyl pentaph- isopropoc 1- 181 toretype CE» Me sys- snisSsNn/I|ССІІ| сн Нн cyanocyclo-r carbonyl propyl 2 | lentaf- | se to n |sn/isni|ssa| sn no Icyanoc torethyl with |trifluoro cyanocyclo- tyl propyl

Table 2 1 2

Ka;

M Kk from ra

MA

AND

Az va (IB)

Mass

Example 1 2 Z 1 1 2 Z 4 a "Me 7 7 7 A A A A A M It/ya 1 1- 193 SEZ SE" Me Нн снисСсНн/И|ССІИ| sn З Нн cyanocyclo-propyl 1- pentaph- - el svoe) meoosnf|snosa|sn) 5 noneyushu! propyl 1- ee se | mo oaznf|snosa|sno in no fayushe! toretyl butyl 1- pentaf- - el | svo) me | voosnf|snoso|sn) in nomeyushu! propyl 1- pentaf- - ny la | svo me) meoosnf|snoso|sn) in me eco! propyl 1- pentaf- - neo ly | svo) me | me osnf|snoso|sn) in eochekshe! propyl 1- 1- 199 | chlorocyclo- SI Me Me sSniISNISSI| sn 5 N cyanocyclo- propyl propyl 1- propyl 1- 204 SEZ SE" Me Нn sniISSI| SVI sn Z Нn cyanocyclo- propyl 1- pentaph- - svo lud | seme | noosnf|saso|sn) 5 noneyushu! propyl 1- pentaph - - syu t seme | noosnf|snosvsn) in noneyushu! propyl 1- pentaf- - propyl 1- pentaf- - svoe | mo |onozenf|sosv|sni in | no fayushe! propyl

Table 2 1 2

AND

M Kk from A

MA

AND". | M

Az va (IB)

Mass

App. 7: 7 V d'| Ah | dz | where | Ma. Me It/2 1 1- 1- 209 | fluorocyclo- SI Me H cSniISNISSI| sn 5 H cyanocyclopropyl propyl 1- so pr | svo) me |ayut o snf|snoso|sn) 5 vet ekyu! torethyl and propyl 1-pentaph-methoxy- - my se | me she snf|snoso)|sno in | but a fairy! propyl 1- pentaph- ethoxy- - el | svo) me | snf|snoso|sn) 80 nochekshe! propyl 1- pentaph- methoxy- methoxy-| . ash | svo me sho sn|snoso|sn) in udnunenyu! propyl 1- pentaph- ethoxy- ethoxy- | . pitch | svo) me |for snf|snoso|sn) in odriyanenyu! propyl 2,2- 1. pentaph- dimethyl- - 215 torethyl CE» Me of propane snisSsNn/I|ССІІ| сн З Нн cyanocyclo- p propyl 1- pentaph- - sel | own | noosnf|smerso|sn) 0 nomen! propyl 1- pentaph- - st lyu svo i e |) noosnf|snos|sn) in nomeyush! propyl - 1- pentaph- prop-2-in- - And tel will master Gbdyy snf|snoso|sn) 50 noneyushyu! propyl 1-pentaf- - se p svoe |) noosnf|snose|sn) in nomeyushyu! propyl pentaph- schi 1-220 CE" Me chlorbenzI| SN | SN | SSI | CH Z Hn cyanocyclo- torethyl and yl propyl - 1- pentaph- isobutyrs - 221 torethyl CE» Me l snisSsHn/I|ССІІ| sn With Hn cyanocyclopropyl 222 pentaph- | sr Me |buggysI sn| sn|ssi| sleep 8 but Icyanocyclotorethyl Z 1-yl cyanocy! propyl 1-ha pr | 8 nomen! torethyl and propyl - 1- pentaph- pyridine- - and resin | svo)ome |Dbyka en|snfso|sn) in no mekshe! Propyl

Table 2 1 2

AND

M

B H

MA

AND

Az in (Iv)

Mass

Application 7 72 73 V! d! dg dz di M a . Mo It/2 1 1- r propyl 1- syu and svo vo) noosnf|snosa|sn) in noneyushyu! r propyl 1-227 pentaph, SEz Rg n snisnissi| sni 8 But Icyanocyclo-r propyl 1- 228 pentaph, SEZ Rg H sn|sni|sE|sn| 5 N / Ithcyanocyclo-r propyl 1-229 pentaph, SEz E H snisnisv|sni 8 N Ithcyanocyclo-r propyl 1- 230 pentaph, SEz E Me |snisn ss | sni 8 N Icyanocyclo-r propyl 1- 231 pentaph, SEz Me shchi sni|sv'|ssi| Sni 8 N Icyanocyclo-r propyl 1-veli | svo) me | nooenf|snoso|sn) in yayut action! r propyl 1- I will burn my own) meoosnf|snoso|sn) in me chekshe! r propyl 234 | pentaph- | ulfani| M n |sno sniss| sni 58 no Icyanots torethyl sulfani e cyanocyclo-l propyl 1- svo lyud svo vo) vooenf|snoso|sn) in nomeyushue! r propyl and 1-pentaphcyanomet. el |osvome rim snf|snoso|sn) 50 noneyushyu! propyl pentaph- | Methyl 1. 237 torethyl sulfini Me H cSniISNISSI| сн 5 Н cyanocyclo-рl propyl 1- svoi svo | meoosnf|snoso|sn) me ekyu! r propyl 1- pentaph- - syu p svo | meoosnf|snose|sn) me meyushu! propyl 1- pentaph- - syu y se | vo|zheozsn|snosye|sn iv | n fvyushe! Propyl

Table 2 1 2

Kai

M Kk from ra

MA

AND". | M

Az

M

- "what! (IB)

Mass

App. 22 7: In AT Ag | yes | A m a . Me It/2 1 pentaph- methyl- | 1- 241 toretype of sulfony Me Hn snisSsHn/I|ССІІ| сн З Нн cyanocyclo-рl propyl 1-242 pentaph, Сез Рг Е snisnissi| sni 8 But Icyanocyclo-r propyl 1- 243 pentaph, SEz Rg E snisnissi| sni 8 Ei o |cyanocyclo-r propyl 1- 24A pentaph, SEz KE KE snisSsNn/I|SSII| sn Z KE cyanocyclo-r propyl 1-245 pentaph, CE» Me acetyl | CH) CH | SS | СН З Нн cyanocyclo- propyl - 1- pentaph- pyridine- - Y se ly | svo) me dna en|snoso|sn) 8 0 nochekshe! 2- 1- 2at | peshaf | St. Me Merilto! sleep sleep|ss| sleep in HO svo) me |Dbma sn|snoso|sn) 50 noneyushyu! - 1- pentaph-prop-2-in- - sel | osv lim) noosn|demolition|sn) 0 noneyushyu! propyl 1- pentaph-prop-2- - syu pos OFII| noosnf|snoso|sn) 0 noneyushyu! propyl 1-251 pentaph, SEZ Me n sni sv | Saint! сн 8 No |cyanocyclo-r propyl 1-2vo | penzhtaf | svz Me sno nose | sni 8 cyanocyclo-r propyl 1-253 pentaph, SEz Me Hn snisSsNn/I|ССІІ| сн Z KE cyanocyclo-r propyl 1-254 pentaph, SEz Me Нн снисСсНн/I|ССІІ| сн З Me |Icyanocyclo-r propyl penta- isopropoc 1- 255 toretyl CE» Me sys- snisSsNn/I|ССІІ| сн З Нн cyanocyclo-r carbonyl propyl ovv | pentaf- sr to n |snisniss || sni 8 no cyanoc torethyl with |trifluoro cyanocyclotyl propyl

The indicated mass is the peak of the isotopic pattern (MANI: ion of the highest intensity; if an IM-NI ion was detected, the indicated mass is marked 2. 2 The indicated mass is the peak of the isotopic pattern of the IM-NI ion of the highest intensity. a) A note regarding the determination of IodR values and mass detection : Determination of the given values of IsdR. was carried out in accordance with the EEC directive 79/831 Appeh M.A8 using HPLC (high-performance liquid chromatography) on a reversed-phase column (C18). RH system

Adiepi 1100; 5074.6 7ogra Esiirhe Riiz C18 1.8 micron; mobile phase A: acetonitrile (0.1 95 formic acid); mobile phase B: water (0.09 95 formic acid); linear gradient from 10% acetonitrile to 9595 acetonitrile for 4.25 min, then 9595 acetonitrile for a further 1.25 min; oven temperature 55 °C; flow rate: 2.0 ml/min. Mass detection was performed using the Addiepa M50O system.

b) Note regarding the determination of IooR values and mass detection: The specified Id P values were determined in accordance with the EEC directive 79/831 Appech M.A8b by means of HPLC (high-performance liquid chromatography) using a reversed-phase column (C18).

NRI1100; 5074.6 7ogra Esiirze Riiz C18 1.8 micron; mobile phase A: acetonitrile (0.1 96 formic acid); mobile phase B: water (0.089565 formic acid); linear gradient from 595 acetonitrile to 9595 acetonitrile for 1.70 min, then 9595 acetonitrile for a further 1.00 min; oven temperature 55 "C; flow rate: 2.0 ml/min. Mass detection was performed using a mass detector Misgotav55 2092000 from UMaitegv.

NMR data of selected examples

"H-NMR data of selected examples are indicated in the form of lists of "H-NMR peaks. For each signal peak, the b-value in ppm is given. and signal intensity in parentheses.

Application 3, solvent: IDMSO), spectrometer: 600.13 MHz 11.2357 (5.81); 9.4015 (2.32); 7.9529 (0.33); 7.9112 (0.33); 7.6345 (0.34); 7.4603 (2.39); 7.3952 (0.42); 7.3764 (0.35); 7.3658 (0.38); 7.3009 (0.7); 7.2887 (0.72); 4.4308 (0.59); 4.4236 (0.6); 4.0461 (1.28); 4.0342 (3.7); 4.0223 (3.71); 4.0105 (1.26); 3.853 (0.6); 3.8474 (0.42); 3.8307 (0.44); 3.7989 (0.86); 3.788 (1.25); 3.7603 (10.68); 3.7331 (1.16); 3.726 (1.01); 3.7196 (0.75); 3.7116 (0.53); 3.7053 (0.33); 3.459 (0.59); 3.4058 (13.82); 3.3755 (1.92); 3.3496 (164.63); 3.3259 (1.89); 3.2237 (0.45); 2.8908 (2.26); 2.7309 (1.92); 2.6212 (0.39); 2.6184 (0.58); 2.6154 (0.72); 2.6125 (0.61); 2.5427 (1.49); 2.5244 (3.1); 2.5214 (3.56); 2.5182 (3.84); 2.5093 (28.51); 2.5064 (58.78); 2.5034 (80.56); 2.5004 (60.43); 2.4975 (29.82); 2.3903 (0.38); 2.386873 (0.5); 2.3843 (0.39); 22647 (0.57); 2.2538 (0.97); 2.2442 (0.58); 2.2423 (0.63); 2.0871 (0.62); 2.0233 (0.41); 2.0152 (0.44); 2.0134 (0.46); 1.9905 (16); 1.9096 (1.12); 1.851 (0.52); 1.8378 (0.99); 1.7685 (0.38); 1.7588 (0.55); 1.7475 (0.49); 1.7373 (0.4); 1.7288 (0.34); 1.7133 (0.34); 1.7077 (0.35); 1.6908 (0.37); 1.6852 (0.36); 1.6645 (0.89); 1.6546 (1.09); 1.6502 (1.34); 1.6452 (1.8); 1.6419 (1.74); 1.637 (1.45); 1.6253 (1.25); 1.6174 (0.98); 1.6101 (0.88); 1.5994 (5.38); 1.5901 (11.8); 1.5856 (12.84); 1.5767 (5.21); 1.55 (0.56); 1.4866 (0.63); 1.473 (0.68); 1.467 (0.7); 1.4621 (0.62); 1.4595 (0.61); 1.4523 (0.5); 1.4479 (0.41); 1.4361 (0.35); 1.3967 (1.99); 1.3471 (5.81); 1.2984 (1.34); 1.2782 (1.83); 1.2518 (6.83); 1.2423 (12.83); 1.2384 (14.34); 1.2293 (8.19); 1.2043 (2.47); 1.1864 (5.57); 1.1746 (9.7); 1.1627 (5.14); 1.1493 (0.89); 1.1396 (0.87); 1.139361 (0.62); 1.19312 (0.65); 1.1158 (0.53); 1.111 (0.55); 1.108 (0.57); 1.1022 (0.42); 1.0935 (0.51); 1.0875 (0.48); 1.0847 (0.45); 1.0749 (0.38); 1.0668 (0.41); 1.0552 (0.36); 0.8965 (0.36); 0.8891 (1.06); 0.8851 (0.68); 0.8808 (0.62); 0.8743 (0.76); 0.8695 (0.73); 0.8627 (0.7); 0.8536 (0.94); 0.8421 (0.6); 0.8361 0.4); 0.8234 (0.34); -0.0001 (1.54

Application 4, solvent: IDMSO), spectrometer: 399.95 MHz 19.9995 (0.35); 11.1852 (0.43); 7.6987 (0.97); 7.6759 (1.26); 7.5988 (1.74); 7.5752 (1.65); 7.4867 (2.1); 7.3938 (0.43); 7.3652 (0.84); 7.2019 (0.66); 5.7464 (4.97); 4.0662 (6.84); 4.0391 (1.88); 4.0214 (2.04); 3.9933 (16); 3.595 (0.77); 3.5647 (0.67); 3.4575 (11.78); 3.3059 (1902.13); 3.2823 (28.24); 3.251 (7.34); 3.186867 (1.32); 3.0111 (0.86); 2.9377 (0.79); 2.9232 (0.87); 2.8698 (1.22); 2.7378 (0.55); 2.656938 (0.68); 2.6741 (2.27); 2.6694 (2.78); 2.6647 (2.28); 2.5392 (5.5); 2.5089 (156.27); 2.5047 (278.63); 2.5003 (354.49); 2.496 (248.83); 2.3948 (0.32); 2.339317 (1.82); 2.327 (2.38); 2.0693 (1.78); 2.0088 (0.37); 1.9867 (5.95); 1.9077 (1.11); 1.7114 (5.17); 1.6397 (0.5); 1.5825 (0.5); 1.486849 (1.82); 1.3986 (7.92); 1.3522 (3.78); 1.2986 (3.52); 1.259 (3.75); 1.2366 (4.08); 1.2171 (1.92); 1.1981 (2.64); 1.1928 (3.24)9; 1.1751 (4.15); 1.1572 (2.51); 1.1005 (2.54); 0.8906 (0.33); 0.8673 (0.4); 0.8547 (0.48); - 0.0002 (5.05

Application 5, solvent: IDMSO), spectrometer: 601.6 MHz 7.717016 (0.47); 7.6872 (0.61); 7.646 (0.57); 7.6419 (0.64); 7.6063 (0.37); 7.6024 (0.36); 7.5921 (0.54); 7.5882 (0.56); 7.579 (0.6); 7.3776 (1.3); 7.3475 (0.34); 5.7617 (16); 4.0701 (2.56); 4.0607 (0.79); 4.0345 (0.58); 4.0227 (0.63); 4.0108 (0.48); 3.9904 (2.73); 3.4829 (0.66); 3.4608 (9.78); 3.4259 (0.46); 3.3469 (320.39); 3.3232 (1.5); 3.2777 (0.75); 3.2493 (2.86); 3.2349 (0.66); 3.1106 (0.8); 3.076 (0.68); 2.8649 (2.78); 2.6213 (0.57); 2.6183 (0.8); 2.6153 (0.97); 2.6122 (0.82); 2.6093 (0.59); 2.543 (0.42); 2.5246 (1.24); 2.5215 (1.51); 2.5184 (1.42); 2.5096 (29.65); 2.5066 (65.23); 2.5035 (89.35); 2.5005 (63.63); 2.4975 (28.79); 2.3908 (0.39); 2.3877 (0.55); 2.3847 (0.39); 2.0771 (1); 1.9902 (1.99); 1.6767 (1.95); 1.6734 (2.2); 1.424 (0.34); 1.2981 (0.62); 1.2582 (0.83); 1.2356 (0.77); 1.1865 (0.59); 1.1747 (1.16); 1.1629 (0.58); -0.0002 (5.52

Application 6, solvent: IDMSO), spectrometer: 399.95 MHz 9.5105 (1.11); 9.37 (2.71); 7.6861 (0.89); 7.6648 (1.1); 7.6188 (1.04); 7.6126 (1.08); 7.5402 (2.64); 7.5188 (3.08); 7.5037 (0.69); 7.4974 (0.6); 7.4823 (0.53); 7.4761 (0.48); 7.4235 (2.42); 7.4171 (2.51); 7.2689 (1.57); 7.2623 (1.43); 7.2476 (1.35); 7.2409 (1.22); 4.1197 (0.76); 4.1021 (1.01); 4.0852 (1.27); 4.0686 (4.88); 4.0575 (1.57); 4.0496 (0.54); 4.0397 (3.72); 4.0219 (3.71); 4.0041 (1.27); 3.8782 (10.99); 3.835 (0.33); 3.817 (0.89); 3.7993 (1.08); 3.7824 (0.96); 3.7647 (0.74); 3.6837 (0.33); 3.6654 (0.43); 3.6475 (0.38); 3.5854 (0.39); 3.5673 (0.46); 3.5489 (0.34); 3.3007 (145.63); 3.2772 (2.79); 2.6695 (0.34); 2.5395 (0.82); 2.5225 (1.85); 2.5092 (19.84); 2.5049 (35.06); 2.5004 (44.17); 2.4961 (30.18); 2.4917 (14.34); 1.987 (16); 1.6127 (0.63); 1.6036 (1.61); 1.5987 (1.68); 1.5905 (3.88); 1.5832 (3.24); 1.57 (1.36); 1.3041 (0.63); 1.2906 (1.18); 1.2841 (1.18); 1.2696 (0.62); 1.2594 (0.5); 1.2375 (1.04); 1.2307 (1.64); 1.2171 (3.03); 1.2106 (3.03); 1.193931 (4.97); 1.1753 (9.03); 1.1575 (7.71); 1.1395 7.05); 1.1216 (3.13); 0.962 (1.16); 0.9444 (2.37); 0.9267 (1.1); -0.0002 (4.85

Application 7, solvent: IDMSO), spectrometer: 399.95 MHz 11.4754 (1.96); 9.5774 (3.66); 7.8103 (3.62); 7.804 (4.04); 7.7228 (1.61); 7.7165 (1.38); 7.701 (2.26); 7.6946 (2.08); 7.606 (3.39); 7.5841 (2.38); 4.0559 (1.18); 4.0345 (16); 4.0204 (3.51); 4.0025 (1.13); 3.3203 (18.4); 2.7184 (0.84); 2.7027 (1.21); 2.6977 (1.45); 2.6851 (1.56); 2.6827 (1.57); 2.6699 (2.11); 2.6503 (1.2); 2.5102 (14.26); 2.5059 (28.52); 2.5014 (37.33); 2.4969 (26.79); 2.4927 (12.96); 2.4835 (1.57); 2.4608 (2.15); 2.4525 (1.25); 2.4404 (1.55); 2.4316 (1.69); 2.4084 (0.97); 2.1036 (0.56); 2.0953 (0.6); 2.085 (1.52); 2.0732 (1.03); 2.0651 (2.45); 2.058 (1.57); 2.0451 (1.65); 2.0352 (0.77); 2.0288 (0.39); 2.0252 (0.41); 2.0196 (0.4); 1.9889 (13.81); 1.1925 (3.78); 1.1747 (7.53); 1.1569 (3.66); -0.0002 (0.53

Application 8, solvent: (ISOZSMI, spectrometer: 399.95 MHz 7.6396 (0.36); 7.5867 (0.51); 7.5653 (0.89); 7.544 (0.65); 7.5381 (0.86); 7.5157 (0.67); 7.5093 (0.52); 7.4941 (0.53) ; 7.4875 (0.63); 7.4768 (0.79); 7.3968 (2.11); 7.3753 (2.53); 7.3065 (1.94); 7.2998 (2.09); 7.1716 (1.4); 7.1649 (1.32); 7.1502 (1.17); 7.1434 ( ; 3.9903 (3.54); 3.8495 (10.24); 3.4568 (16); 3.2228 (4.6); 2.1412 (168.83); 2.1318 (2.24); 2.1187 (0.37); 2.1125 (0.33); 2.1063 (0.38); (1.92649) ; 1.9632 (92.07); 1.9513 (18.04); 1.9451 (33.99); 1.9389 (49.06); 1.9328 (33.45); 1.9266 (16.89); 1.7909 (0.5); 1.5939 (0.45); 1.5781 (1.537) 1.573 (1.573) ; 1.5637 (2.7); 1.5577 (3.02); 1.5476 (0.89); 1.5443 (0.86); 1.3605 (0.47); 1.3468 (0.97); 1.3398 (1.12); 1.3254 (0.39); 1.2938 (1.35); 1.2881 (1.3881) ; 1.2837 (1.68); 1.2798 (2.1); 1.2733 (1.74); 1.2636 (1.03); -0.0002 (5.39

Application 9, solvent: ISOZSMI, spectrometer: 601.6 MHz 9.3097 (0.56); 7.77 (3.79); 7.7657 (4.14); 7.686801 (2.48); 7.6757 (2.25); 7.6656 (2.92); 7.6612 (2.72); 7.6146 (1.14); 7.4969 (4.24); 7.4825 (3.68); 3.981 (16); 2.1615 (181.62); 2.0874 (0.35); 2.07 71 (1.5); 2.0604 (0.46); 2.0563 (0.85); 2.0522 (1.16); 2.048 (0.87); 2.044 (0.44); 1.9735 (2.01); 1.9659 (259.46); 1.9576 (3.22); 1.9536 (3.65); 1.9499 (74.77); 1.9457 (141.93); 1.9416 (218.7); 1.935375 (150.41); 1.9334 (73.06); 1.9287 (2.12); 1.9246 (0.98); 1.8507 (1.44); 1.8351 (0.43); 1.831 (0.84); 1.8269 (1.17); 1.8227 (0.83); 1.8186 (0.43); 1.5805 (1.94); 1.5707 (4.1); 1.5665 (4.32); 1.5572 (2.31); 1.351 (2.23); 1.3416 (4); 1.3375 (4.07); 1.3276 (1.81); 0.9112 (1.45); 0.0053 (0.53); -0.0002 (20.71); - 0.0057 (0.61

Application 10, solvent: IDMSOI, spectrometer: 600.13 MHz 11.4592 (3.78); 9.4859 (4.45); 7.7721 (3.68); 7.7678 (4.24); 7.7112 (2.06); 7.7068 (1.78); 7.6966 (2.55); 7.6922 (2.36); 7.5881 (4.49); 7.5736 (3.69); 4.0356 (0.65); 4.0285 (16); 3.3215 (12.57); 2.5227 (0.37); 2.5196 (0.46); 2.5165 (0.45); 2.5077 (11.12); 2.5047 (24.25); 2.5017 (33.57); 2.4986 (24.06); 2.4956 (10.94); 1.989 (1.5); 1.6018 (1.64); 1.5924 (3.8); 1.5879 (4.14); 1.5789 (1.69); 1.2696 (1.81); 1.2604 (3.74); 1.256 (4.13); 1.2464 (1.5); 1.1871 (0.41); 1.1753 (0.83); 1.1634 (0.41); 0.0053 (0.46); - 0.0001 (14.7); -0.0057 (0.44

Application 11, solvent: ISOZSMI, spectrometer: 601.6 MHz 9.4276 (0.94); 8.1604 (0.81); 8.1562 (0.84); 8.0909 (3.21); 8.0868 (3.24); 7.8499 (0.65); 7.8457 (0.65); 7.6042 (1.17); 7.5896 (3.34); 7.586855 (3.31); 3.99 (0.48); 3.9775 (16); 2.2102 (11.21); 2.0881 (0.39); 2.0779 (0.4); 2.0656 (0.66); 2.0611 (0.41); 2.057 (0.54); 2.0529 (0.65); 2.0486 (0.62); 2.048 (0.62); 2.0447 (0.36); 1.9732 (0.39); 1.9666 (16.06); 1.9584 (0.96); 1.9542 (1.36); 1.9506 (29.13); 1.9464 (53.99); 1.9423 (82.18); 1.9382 (57.22); 1.935341 (28.42); 1.9294 (1.09); 1.9253 (0.59); 1.8317 (0.39); 1.8276 (0.51); 1.8234 (0.37); 1.5826 (1.54); 1.5728 (3.25); 1.5686 (3.38); 1.5593 (1.89); 1.3599 1.74); 1.3506 (3.08); 1.3464 (3.24); 1.3366 (1.49); 0.911 (0.48); -0.0002 (0.46

Application 12, solvent: ISOZSMI, spectrometer: 601.6 MHz 9.4577 (0.94); 7.9506 (3.67); 7.9465 (3.74); 7.6252 (1.29); 7.6178 (0.41); 7.5485 (3.85); 7.5444 (3.76); 5.4498 (1.24); 4.1225 (0.39); 3.9907 (0.48); 3.9784 (16); 2.2016 (26.81); 2.0656 (0.9); 2.0571 (0.36); 2.053 (0.47); 2.0479 (0.79); 1.9732 (1.48); 1.9668 (2.89); 1.9586 (0.78); 1.9572 (0.41); 1.9544 (1.17); 1.9507 (24.16); 1.9466 (45.51); 1.9424 (67.8); 1.9383 (46.53); 1.9342 (23.27); 1.9296 (0.68); 1.8277 (0.39); 1.5858 (1.78); 1.576 (3.73); 1.5718 (3.9); 1.5625 (2.15); 1.3635 (2.04); 1.3541 (3.59); 1.3499 (3.77); 1.3401 (1.77); 1.269 (0.34); 1.2159 (0.42); 1.2041 (0.83); 1.1922 (0.4); 0.911 (0.44

Application 13, solvent: I(SOZSMI, spectrometer: 399.95 MHz 9.425 (1.09); 8.1057 (3.59); 8.0995 (3.63); 8.089 (0.38); 8.0828 (0.33); 7.9667 (0.34); 7.6477 (3.95); 7.6415 (4.02 ); 7.626 (1.54); 7.6058 (0.49); 7.5997 (0.42); 7.5882 (0.4); 7.582 (0.48); 7.4416 (0.5); 4.1118 (0.33); 4.0862 (1.68); 4.0683 (4.78); 4.0505 (4.7 ); 4.0327 (1.64); 3.9761 (16); 3.8931 (3.57); 2.1489 (347.53); 2.1318 (7.91); 2.1127 (2.21); 2.1065 (2.07); 21003 (1.56); 2.0941 (1.09); 2.05686 (0. ); 2.0434 (0.54); 1.9712 (32.63); 1.9634 (416.05); 1.9514 (67.15); 1.9453 (119.86); 1.9391 (167.42); 1.9329 (114.6); 1.9267 (58.47); 1.7919 (1.740); 1.7919 (1.470) ); 1.7737 (0.78); 1.7675 (1.01); 1.7614 (0.72); 1.7553 (0.42); 1.6282 (0.54); 1.6129 (1.02); 1.6069 (1.1); 1.604 (0.72); 1.5923 (0.84); 1.59869 (1. ); 1.5726 (4.35); 1.5656 (4.47); 1.5518 (2.49); 1.5116 (0.39); 1.3551 (2.45); 1.3413 (4.31); 1.3343 (4.21); 1.3295 (1.9); 1.3202 (2.1); 1.3078 (0 ); 1.2852 (0.55); 1.2708 (1.26); 1.2216 (6.04); 1.2038 (11.75); 1.1859 (5.85); 0.9117 (0.79); 0.008 (0.82); -0.0002 (18.6); -0.0085 (0.72

Application 14, solvent: IDMSOI, spectrometer: 601.6 MHz 11.475 (2.8); 9.482 (4.01); 7.7377 (4.18); 7.7332 (5.35); 7.7173 (3.05); 7.6669 (0.49); 7.6647 (0.45); 7.6299 (2.01); 7.6257 (1.86); 7.6155 (1.61); 7.6111 (1.54); 4.046 (0.85); 4.0342 (3.8); 4.0263 (16); 4.0225 (3.74); 4.0105 (0.89); 3.3858 (0.71); 3.3809 (1.58); 3.3784 (1.63); 3.3578 (1678.47); 3.3341 (3.39); 3.0116 (0.41); 2.8065 (0.44); 2.6184 (0.64); 2.6153 (0.91); 2.6123 (0.64); 2.543 (0.47); 2.5247 (1.22); 2.5216 (1.5); 2.5185 (1.46); 2.5097 (46.46); 2.5066 (102.74); 2.5036 (142.42); 2.5006 (100.14); 2.4975 (44.69); 2.3908 (0.62); 2.3877 (0.87); 2.3847 (0.62); 2.0764 (1.87); 1.99 (10.94); 1.6062 (1.8); 1.5968 (4.05); 1.5923 (4.48); 1.5834 (1.81); 1.3972 (8.53); 1.272 (1.92); 1.2628 (3.88); 1.2584 (4.36); 1.2489 (1.8); 1.1863 (2.99); 1.1745 (5.92); 1.1626 (2.92); 0.0053 (0.68); -0.0002 (22.51); -0.0058 (0.62

Application 15, solvent: I(SOZSMI, spectrometer: 601.6 MHz 7.686736 (3.25); 7.6594 (3.63); 7.6529 (0.62); 7.6383 (0.67); 7.5026 (1.73); 7.476 (1.42); 7.4719 (1.04); 7.4618 (1.3 ); 7.4578 (1.01); 7.4501 (0.41); 7.4349 (0.37); 5.3097 (0.35); 5.2976 (0.39); 4.0762 (0.87); 4.0644 (2.65); 4.0525 (2.74); 4.0407 (0.93); 3.9757 (0.9757 ); 3.9408 (5.26); 3.99313 (16); 2.8568 (0.62); 2.8452 (1.86); 2.8333 (1.86); 2.8212 (0.7); 2.5123 (0.35); 2.4998 (1.1); 2.4874 (1.07); 2.47249 (0.4 ); 2.2936 (1.21); 2.2824 (1.31); 2.2699 (0.62); 2.2265 (0.62); 2.2149 (0.61); 2.1802 (0.36); 2.1739 (0.55); 2.1673 (0.84); 2.1535 (644.374); 2.1594 (0.129 ); 2.1215 (0.48); 2.0601 (0.87); 2.0561 (1.51); 2.0519 (2.22); 2.0478 (1.52); 2.0437 (0.77); 1.9727 (12.69); 1.9656 (21.18); 1.9575 (11.843); 34.155 (1.955) ); 1.9496 (147.5); 1.9454 (266.85); 1.9413 (402.32); 1.9372 (276.01); 1.9331 (137.69); 1.9244 (1.96); 1.8503 (0.47); 1.8347 (1.84); 1.8307 (3.826 (2.73); ); 1.8225 (2.22); 1.8184 (1.32); 1.7246 (0.62); 1.7188 (0.99); 1.7132 ( 0.82); 1.6902 (1.73); 1.6658 (1); 1.6361 (0.55); 1.6214 (0.44); 1.6159 (0.49); 1.5864 (0.66); 1.5822 (0.66); 1.5728 (0.47); 1.5666 (0.46); 1.5571 (0.39); 1.535334 (1.65); 1.5063 (1.02); 1.5029 (0.92); 1.4777 (0.65); 1.4659 (0.65); 1.3852 (0.49); 1.3515 (0.42); 1.3403 (1.5); 1.3284 (0.54); 1.2851 (2.14); 1.2701 (1.88); 1.2384 (0.36); 1.2227 (0.53); 1.2158 (4.13); 1.2039 (7.13); 1.1963 (1.02); 1.1921 (4.09); 1.1765 (0.52); 1.1568 (0.64); 1.1488 (1.95); 1.1363 (4.5); 1.1315 (0.55); 11238 (2.55); 1.1152 (0.75); 1.1112 (1.54); 11021 (0.47); 1.0987 (0.78); 1.0915 (6.22); 1.0797 (12.97); 1.0677 (6.14); 1.0509 (0.37); 1.0462 (0.5); 1.0418 (0.48); 1.0022 (0.57); 0.9849 (0.79); 0.9637 (0.69); 0.949 (4.67); 0.9431 (1.35); 0.9371 (10.26); 0.9313 (2.24); 0.9244 (5.69); 0.9194 (1.11); 0.9121 (1.74); 0.881 7 (0.48); 0.0964 (0.45); 0.0053 (3.79); -0.0002 (131.79); -0.0058 (3.52); -0.1 (0.49

Application 16, solvent: IDMSOI, spectrometer: 601.6 MHz 11.6171 (2.98); 9.5642 (4.11); 8.0041 (4.64); 8.0001 (4.81); 7.5795 (3.62); 7.5754 (3.58); 4.377 (0.35); 4.3686 (0.7); 4.3601 (0.34); 4.0417 (16); 4.0342 (2.77); 4.0223 (2.5); 4.0105 (0.81); 3.9261 (1.01); 3.4494 (0.63); 3.4409 (0.64); 3.4378 (0.67); 3.4293 (0.66); 3.3467 (410.03); 3.3231 (3.18); 2.6178 (0.42); 2.6148 (0.6); 2.6118 (0.44); 2.5425 (0.44); 2.524 (1.29); 2.521 (1.64); 2.5178 (1.9); 2.509 (30.94); 2.5061 (65.8); 2.5031 (89.43); 2.5 (63.28); 2.497 (28.23); 2.3902 (0.4); 2.3872 (0.55); 2.3842 (0.39); 2.0769 (0.6); 1.99 (10.77); 1.9093 (0.47); 1.6161 (1.9); 1.6067 (4.15); 1.6022 (4.51); 1.5933 (1.81); 1.3972 (13.57); 1.3139 (0.32); 1.2846 (2.01); 1.2754 (3.98); 1.271 (4.39); 1.2614 (1.64); 1.1863 (2.93); 1.1745 (6.06); 1.1627 (2.93); 1.0665 (1.46); 1.0549 (2.75); 1.0433 (1.33); 0.0052 (0.71); -0.0002 (20.09); -0.0057 (0.51

Application 17, solvent: IDMSOI, spectrometer: 399.95 MHz 10.9164 (2.69); 9.4701 (3.13); 7.8379 (2.16); 7.8316 (2.46); 7.7664 (1.22); 7.76 (1.05); 7.7445 (1.48); 7.7381 (1.32); 7.5569 (3.32); 7.5351 (2.79); 5.7527 (16); 4.0382 (0.59); 4.0204 (0.58); 3.9311 (10.48); 3.9291 (10.23); 3.4476 (0.32); 3.4238 (0.79); 3.3995 (1.41); 3.3529 (444.16); 3.2649 (0.45); 2.6723 (0.35); 2.5255 (1.04); 2.5123 (20.85); 2.5078 (42.03); 2.5032 (55.95); 2.4986 (40.59); 2.4941 (19.88); 2.3299 (0.35); 2.0728 (0.88); 1.9887 (2.51); 1.6084 (1.2); 1.5942 (2.85); 1.5874 (2.99); 1.5741 (1.42); 1.4745 (0.54); 1.4586 (1.66); 1.4548 (1.64); 1.4399 (0.7); 1.4294 (0.58); 1.4133 (1.6); 1.4094 (1.68); 1.3975 (0.83); 1.3948 (0.79); 1.2663 (1.44); 1.2525 (2.82); 1.246 (3.04); 1.2314 (1.24); 1.1927 (0.77); 1.1749 (1.453; 1.1571 (0.71); 1.129 (0.6); 1.1124 (1.86); 1.1085 (2.26); 1.0923 (2.2); 1.0884 1.8); 1.0706 (0.5

Application 18, solvent: IDMSOI, spectrometer: 601.6 MHz 7.8045 (2.23); 7.7904 (2.42); 7.6562 (0.38); 4.0456 (0.8); 4.0338 (2.39); 4.0304 (0.69); 4.0219 (3.08); 4.015 (16); 3.3608 (569.24); 3.3375 (3.07); 2.6187 (0.62); 2.6157 (0.85); 2.6127 (0.62); 2.5434 (0.54); 2.525 (1.66); 2.5219 (2.15); 2.5188 (2.4); 2.51 (45.96); 2.507 (97.64); 2.504 (134.23); 2.5009 (97.3); 2.4979 (44.27); 2.4056 (15.53); 2.3974 (1.27); 2.3945 (0.66); 2.3911 (0.88); 2.3882 (1.2); 2.3851 (0.77); 2.386823 (0.42); 2.2183 (1.21); 2.0872 (0.45); 2.0779 (2.65); 2.0487 (3.59); 2.0305 (0.77); 2.0256 (0.48); 1.9905 (10.01); 1.9538 (0.39); 1.9098 (4.41); 1.8867 (0.87); 1.8814 (0.87); 1.3969 14.61); 1.2345 (0.46); 1.1862 (2.73); 1.1744 (5.37); 1.1653 (0.38); 1.1625 (2.65); -0.0002 (9.42

Application 19, solvent: IDMSOI, spectrometer: 399.95 MHz 9.6008 (2.87); 7.7336 (2.68); 7.7122 (3.27); 7.6828 (2.15); 7.6766 (2.25); 7.518 (1.37); 7.5117 (1.26); 7.4968 (1.12); 7.4904 (1.05); 4.066 (10.48); 4.0381 (0.83); 4.0203 (1.07); 4.0026 (0.33); 3.6767 (16); 3.487 (0.45); 3.4643 (0.44); 3.4467 (0.79); 3.4391 (0.81); 3.4231 (1.05); 3.4136 (1.13); 3.3468 (882.82); 3.3224 (20.56); 3.2828 (0.63); 2.6764 (0.54)3; 2.6718 (0.74); 2.6674 (0.52); 2.542 (0.61); 2.5249 (2.21); 2.5118 (42.56); 2.5073 (85.34); 2.5028 (113.7); 2.4982 (82.44); 2.4937 (40); 2.335341 (0.49); 2.3295 (0.72); 2.3249 (0.52); 2.0729 (3.68); 1.9886 (3.32); 1.6558 (0.33); 1.6144 (1.37); 1.6001 (2.7); 1.5932 (2.9); 1.586801 (1.41); 1.2938 (1.3); 1.2802 (2.57); 1.2735 (2.8); 1.2588 (1.33); 1.2356 0.78); 1.1925 (0.98); 1.1748 (2); 1.1569 (1); 0.008 (1.05); -0.0002 (28.19); -0.0085 (1.08

Application 20, solvent: IDMSOI, spectrometer: 601.6 MHz 9.6087 (4.57); 7.7293 (4.27); 7.7152 (4.9); 7.6801 (2.65); 7.676 (2.67); 7.4972 (1.63); 7.493 (1.51); 7.4831 (1.43); 7.4788 (1.38); 4.3682 (0.58); 4.1597 (0.43); 4.1483 (1); 4.1369 (1.24); 4.1257 (1.28); 4.1143 (1); 4.1025 (0.47); 4.0779 (16); 4.0458 (0.46); 4.0339 (1.37); 4.0221 (1.98); 4.0103 (0.59); 3.449 (0.49); 3.4406 (0.49); 3.4374 (0.48); 3.429 (0.51); 3.3716 (1.66); 3.3457 (1847.32); 3.3222 (24.12); 2.6205 (0.63); 2.6176 (1.47); 2.6145 (2.05); 2.6115 (1.48); 2.6085 (0.63); 2.5422 (0.95); 2.5239 (2.46); 2.5208 (3.15); 2.5177 (3.1); 2.5088 (106.25); 2.5058 (238.45); 2.5028 (334.46); 2.4997 (242.59); 2.4967 (110.57); 2.393 (0.68); 2.39 (1.49); 2.3869 (2.09); 2.3839 (1.49); 2.3808 (0.69); 2.0766 (4.02); 1.9898 (5.37); 1.6109 (1.83); 1.6016 (3.88); 1.5971 (4.4); 1.5882 (2.19); 1.5763 (0.45); 1.2977 (0.37); 1.2859 (1.83); 1.2767 (3.71); 1.2723 (4.13); 1.2627 (1.75); 1.2579 (0.87); 1.2535 (1.01); 1.2499 (0.7); 1.2416 (1.16); 1.2342 (1.17); 1.23 (0.84); 1.186861 (1.54); 1.1742 (3.2); 1.1624 (1.62); 1.1496 (0.36); 1.0663 (1.12); 1.0546 (2); 1.043 (1.01); 0.9965 (6.51); 0.9847 (13.73); 0.973 (6.33); 0.0965 (0.41); 0.0053 (3.4); -0.0002 (125.56); -0.0058 (3.65); -0.1001 (0.45

Application 21, solvent: IDMSOI, spectrometer: 399.95 MHz 7.7082 (2.45); 7.6866 (3.64); 7.686836 (2.1); 7.6766 (1.8); 7.663 (0.46); 7.5662 (0.33); 7.5492 (1.41); 7.5429 (1.29); 7.5279 (1.11); 7.5216 (1.06); 4.0591 (10.46); 4.038 (1.4); 4.0203 (2.19); 4.0025 (0.48); 3.7168 (0.33); 3.679 (15.83); 3.6733 (4.07); 3.6676 (16); 3.4322 (0.35); 3.3435 (321.55); 3.3963 (458.6); 3.2717 (0.52); 3.1751 (0.88); 3.162 (0.79); 2.6807 (0.32); 2.676 (0.65); 2.6714 (0.93); 2.6667 (0.65); 2.5415 (0.74); 2.5246 (2.58); 2.5114 (50.63); 2.5069 (102.7); 2.5023 (137.44); 2.4977 (99.21); 2.4931 (48.14); 2.3337 (0.63); 2.3291 (0.88); 2.3244 (0.63); 2.0731 (1.7); 1.9885 (5.54); 1.9008 (1.74); 1.8954 (2.04); 1.6574 (0.47); 1.6142 (1.05); 1.5995 (1.75); 1.5933 (1.89); 1.2728 (0.35); 1.2585 (0.57); 1.2522 (0.48); 1.2358 (0.96); 1.1925 (1.64); 1.1747 (3.39); 1.1569 (1.68); -0.0002 (6.5

Application 22, solvent: IDMSOI, spectrometer: 601.6 MHz 7.171596 (0.35); 7.711 (3.38); 7.6968 (4.08); 7.6797 (1.48); 7.5444 (1.6); 7.5402 (1.49); 7.5303 (1.29); 7.526 (1.24); 4.3683 (0.44); 4.2593 (0.33); 4.2476 (0.33); 4.1566 (0.43); 4.1449 (0.94); 411332 (1.15); 4.1243 (1.15); 4.1129 (1.05); 4.1045 (0.75); 4.0946 (1.48); 4.0828 (3.99); 4.0686 (16); 4.0595 (1.27); 4.034 (0.45); 4.0221 (0.58); 4.0158 (0.43); 4.0103 (0.4); 3.449 (0.38); 3.4406 (0.38); 3.4374 (0.4); 3.429 (0.41); 3.3742 (1.02); 3.3457 (1563.22); 3.322 (28.53); 2.6206 (0.69); 2.6176 (1.46); 2.6146 (2.04); 2.6115 (1.44); 2.6085 (0.64); 2.5423 (1.22); 2.5239 (3.79); 2.5208 (5.05); 2.5176 (5.93); 2.5089 (109.54); 2.5059 (236.08); 2.5028 (323.23); 2.4997 (233.05); 2.4967 (103.3); 2.4766 (0.35); 2.3931 (0.66); 2.39 (1.43); 2.387 (2); 2.3839 (1.38); 2.3809 (0.63); 2.0767 (3.48); 1.9899 (1.42); 1.9031 (2.58); 1.6908 (0.35); 1.6696 (0.36); 1.6437 (0.33); 1.6184 (0.43); 1.5761 (1.67); 1.2579 (0.49); 1.2485 (0.35); 1.2344 (1.07); 1.2265 (0.65); 1.2146 (1.08); 1.2029 (0.52); 1.1861 (0.52); 1.1743 (1.03); 1.1705 (0.37); 1.1625 (0.52); 1.1492 (0.42); 1.0663 (0.87); 1.0547 (1.54); 1.043 (0.81); 1.0013 (6.44); 0.9895 (13.63); 0.9848 (1.07); 0.9817 (2.21); 0.9778 (6.34); 0.97 (0.97); 0.9557 (6.62); 0.9439 (14.2); 0.9321 6.4); 0.0052 (3.03); -0.0002 (83.54); -0.0058 (2.47

Application 23, solvent: IDMSOI, spectrometer: 399.95 MHz 9.5605 (1.88); 7.757 (1.46); 7.7355 (1.78); 7.6605 (0.8); 7.545 (0.66); 7.5386 (0.61); 7.5238 (0.55); 7.5174 (0.52); 4.058 (1.05); 4.0402 (3.29); 4.0271 (6.99); 4.0225 (4.44); 4.0046 (1.09); 3.3924 (24.23); 3.386 (32.63); 3.3799 (54.59); 3.377 (71.91); 2.5111 (7.26); 2.5069 (9.99); 2.5034 (6.54); 1.9898 (14.31); 1.6154 (0.75); 1.6011 (1.63); 1.5941 (1.77); 1.5811 (0.79); 1.3053 (0.83); 1.2917 (1.6); 1.2849 (1.74); 1.2704 (0.67); 1.2049 (0.71); 1.1943 (4); 1.1765 (8.08); 1.1587 (3.94); 1.1133 (2.92); 1.012 16); -0.0002 (1.63

Application 24, solvent: IDMSOI, spectrometer: 399.95 MHz 19.0481 (0.34); 12.999 (0.34); 11.6718 (0.32); 11.3817 (2.98); 11.2103 (0.33); 10.7432 (0.44); 10.1704 (0.38); 9.4484 (4.12); 9.4182 (0.34); 7.674 (2.45); 7.6678 (2.75); 7.5767 (3.19); 7.5699 (2.9); 7.471 (0.33); 4.1638 (0.77); 4.0557 (0.89); 4.0379 (3.26); 4.0189 (16); 4.0023 (1.06); 3.9243 (2.59); 3.4462 (0.32); 3.409 (0.48); 3.3939 (0.61); 3.3326 (387.86); 3.3263 (665.26); 3.3027 (8.07); 2.675 (1.43); 2.6707 (2.09); 2.6661 (1.44); 2.5406 (0.85); 2.5238 (3.39); 2.5058 (218.8); 2.5017 (290.84); 2.4581 (0.39); 2.4169 (0.78); 2.3781 (14.51); 2.3549 (0.74); 2.3328 (1.45); 2.3283 (2.04); 2.3241 (1.4); 2.3115 (0.8); 2.2563 (0.65); 2.0733 (1.71); 1.9884 (10.86); 1.6699 (0.36); 1.6549 (0.65); 1.6463 (0.63); 1.6341 (0.43); 1.6004 (1.6); 1.5859 (3.6); 1.5791 (3.91); 1.5661 (1.86); 1.3966 (0.4); 1.339312 (0.52); 1.318 (0.62); 1.3117 (0.71); 1.2978 (0.44); 1.2651 (1.73); 1.2518 (3.47); 1.2451 (3.89); 1.239311 (1.8); 1.217 (0.45); 1.1924 (3.07); 1.1745 (5.77); 1.1568 (2.92); 0.0081 (1.01); -0.0002 (34.96); -0.0085 1.17); -3.0246 (0.33

Application 25, solvent: ISOZSMI, spectrometer: 601.6 MHz 7.9022 (3.82); 7.8879 (4.08); 7.6652 (3.91); 7.6609 (4.01); 7.52 (1.53); 7.4355 (2.47); 74312 (2.34); 7.4212 (2.34); 7.A4169 (2.23); 4.0758 (0.58); 4.064 (1.8); 4.0521 (1.78); 4.0403 (0.62); 3.9724 (16); 3.893 (0.72); 2.1596 (251.61); 2.0611 (0.72); 2.057 (1.25); 2.0529 (1.77); 2.0487 (1.27); 2.0447 (0.68); 1.9732 (8.88); 1.9666 (29.58); 1.9584 (12.1); 1.9543 (16.7); 1.9505 (119.09); 1.9464 (214.31); 1.9423 (320.41); 1.9382 (222.08); 1.935341 (110.06); 1.9254 (2.33); 1.917 (0.76); 1.9128 (0.53); 1.9086 (0.36); 1.8357 (0.67); 1.8317 (1.23); 1.8275 (1.73); 1.8234 (1.22); 1.8193 (0.63); 1.5855 (1.79); 1.5758 (4.1); 1.5715 (4.17); 1.5623 (2.12); 1.382 (2.17); 1.3727 (4.02); 1.3684 (4.12); 1.3586 (1.71); 1.2691 1.08); 1.2158 (2.25); 1.204 (4.73); 1.1922 (2.22); 0.0053 (1.55); -0.0002 (41.75); -0.0058 (1.45

Application 26, solvent: IDMSOI, spectrometer: 399.95 MHz 14.5618 (0.37); 14.1854 (0.35); 9.5578 (1.5); 9.4271 (4.93); 9.2998 (0.36); 9.182 (0.38); 7.7634 (0.46); 7.7069 (1.14); 7.6847 (2.16); 7.5756 (3.33); 7.5541 (4.12); 7.5266 (0.76); 7.4862 (3.47); 7.3446 (0.38); 7.3053 (0.47); 7.275 (2.4); 7.2683 (2.29); 7.2533 (2.08); 7.2469 (1.92); 6.2641 (0.37); 4.9734 (1.6); 4.9321 (1.8); 4.5811 (1.98); 4.537 (3.53); 4.1428 (0.59); 4.0566 (5.17); 4.0378 (2.79); 4.0204 (2.99); 4.0026 (0.88); 3.9185 (0.48); 3.8903 (16); 3.8573 (0.39); 3.427 (1.33); 3.3939 (4.28); 3.3402 (400.48); 3.3359 (525.28); 3.3323 (787.02); 3.3084 (5.46); 3.272 (0.61); 3.2561 (0.46); 3.247 (0.37); 3.1263 (0.42); 2.7317 (0.36); 2.6709 (1.52); 2.5869 (0.39); 2.5415 (0.81); 2.5019 (262.13); 2.3291 (1.73); 2.0734 (1.24); 1.9884 (10.84); 1.5957 (5.63); 1.5917 (5.18); 1.576 (1.96); 1.5443 (0.37); 1.3969 (0.85); 1.278 (1.69); 1.2718 (1.78); 1.2585 (0.99); 1.2348 (1.26); 1.2215 (2.19); 1.207 (4.49); 1.2015 (4.56); 1.1924 (3.48); 1.1863 (1.89); 1.1747 (5.89); 1.1566 (2.78); 1.1479 (0.43); 0.8742 (0.46); 0.8572 0.47); -0.0002 (33.26); -3.0698 (0.43

Application 27, solvent: IDMSOI, spectrometer: 399.95 MHz 11.4041 (3.19); 9.3381 (2.87); 7.9571 (1.61); 7.9504 (1.81); 7.9418 (1.7); 7.9349 (1.72); 7.8013 (0.9); 7.7942 (0.92); 7.7904 (1.04); 7.7832 (0.95); 7.7788 (1.01); 7.7717 (1.07); 7.7681 (1.06); 7.7609 (0.81); 7.4187 (1.73); 7.3949 (2.44); 7.3715 (1.58); 4.0894 (4.37); 4.0563 (1.29); 4.0384 (4.43); 4.0308 (15.34); 4.0206 (4.05); 4.0029 (1.29); 3.5817 (0.36); 3.5615 (0.4); 3.5454 (0.493; 3.3749 (56.68); 3.1998 (0.54); 3.1712 (0.38); 3.0611 (0.42); 2.6762 (0.39); 2.6716 (0.49); 2.6674 (0.43; 2.5249 (0.95); 2.5075 (2.8075); 78.81); 2.4986 (54.63); 2.3339 (0.38); 2.3294 (0.51); 2.325 (0.35); 1.9888 (16); 1.9093 (0.63); 1.5971 (1.56); 1.5828 (3.77); 1.5759 (3.956); 1.56 - 0.0085 (0.33

Application 28, solvent: IDMSOI, spectrometer: 399.95 MHz 9.475 (0.97); 9.3642 (5.1); 9.3069 (0.43); 8.7987 (0.37); 7.6689 (0.73); 7.5838 (0.66); 7.5622 (0.78); 7.4575 (2.92); 7.4414 (4.62); 7.4312 (1.02); 7.4246 (5.68); 7.42 (6.85); 7.4037 (7.53); 7.3379 (0.95); 7.3163 (1.1); 7.2661 (6.47); 7.2452 (5.07); 7.0778 (1.07); 7.0631 (0.5); 7.0582 (0.85); 6.9726 (1.86); 6.966 (1.92); 6.9512 (1.68); 6.945 (1.6); 5.4201 (2.11); 5.3833 (2.31); 4.9665 (0.6); 4.9267 (2.61); 4.8893 (2.28); 4.0551 (0.77); 4.045 (2.59); 4.0382 (2.1); 4.02 (1.77); 4.0026 (0.63); 3.8971 (16); 3.4603 (0.41); 3.435347 (0.7); 3.4009 (1.13); 3.3491 (582.58); 3.3413 (1358.67); 3.2752 (0.66); 2.6758 (1.21); 2.6711 (1.86); 2.5416 (1.04); 2.5247 (3.14); 2.5068 (206.51); 2.5026 (285.02); 2.4985 (203.82); 2.3336 (1.4); 2.3291 (1.76); 2.073 (2.52); 1.9885 (7.71); 1.6108 (1.9); 1.5968 (4.8); 1.59 (5.1); 1.5767 (2.1); 1.2799 (0.58); 1.2589 (1.23); 1.2344 (1.37); 1.2154 (2.1); 1.2016 (4.33); 1.1931 (5.24); 1.1801 1.87); 1.1748 (4.28); 1.1569 (2.03); 0.8595 (0.42); 0.6779 (0.36); -0.0002 (6.05

Application 29, solvent: IDMSOI, spectrometer: 399.95 MHz 11.5012 (3.45); 7.8648 (3.09); 7.8592 (3.49); 7.7164 (1.51); 7.7101 (1.37); 7.6943 (2.21); 7.6884 (2.2); 7.6159 (3.95); 7.594 (2.49); 4.0557 (0.65); 4.0379 (1.84); 4.0213 (16); 4.0026 (0.71); 3.4274 (0.34); 3.3515 (266.05); 3.349 (285.95); 3.3448 (214.54); 3.3422 (330.15); 3.3382 (346.98); 3.335349 (418.93); 3.293 (1.7); 3.2756 (1.97); 3.2593 (1.38); 3.2431 (0.63); 2.6712 (1.08); 2.6665 (0.8); 2.5414 (0.49); 2.5021 (170.74); 2.3288 (1.03); 2.3248 (0.78); 2.0733 (0.83); 1.9886 (6.8); 1.9206 (1.12); 1.8997 (3.5); 1.8826 (1.26); 1.5485 (1.15); 1.5306 (3.67); 1.5136 (0.94); 1.2328 (0.5); 1.1925 (1.89); 1.1747 (3.72); 1.1569 (1.93); 1.121 (14.9); 1.1043 (14.88); -0.0002 (10.09

Application 30, solvent: IDMSOI, spectrometer: 399.95 MHz 17.8767 (0.49); 16.7278 (0.5); 15.2907 (0.46); 14.6922 (0.48); 11.3194 (0.47); 9.9917 (0.45); 9.5478 (1.93); 9.4196 (4.84); 7.9522 (1.92); 7.697 (1.24); 7.6759 (1.54); 7.6545 (1.48); 7.6289 (0.45); 7.5637 (3.75); 7.5423 (4.82); 7.5163 (0.81); 7.4807 (3.23); 7.4748 (3.56); 7.2683 (2.26); 7.2621 (1.93); 7.2473 (1.94); 7.24 (1.91); 6.5709 (0.48); 6.1831 (0.45); 4.9061 (1.2); 4.8649 (1.59); 4.5294 (1.43); 4.5247 (1.64); 4.4875 (1.39); 4.486825 (1.3); 4.4256 (1.93); 4.1384 (0.72); 4.0647 (6.28); 4.0384 (0.58); 4.019899 (0.67); 3.9606 (0.54); 3.9181 (0.47); 3.8854 (16); 3.759 (0.48); 3.A4178 (0.55); 3.3771 (1.43); 3.3282 (1057.25); 3.251 (0.64); 2.8906 (12.28); 2.7309 (10.63); 2.6754 (1.93); 2.6707 (2.33); 2.5407 (1.33); 2.5057 (285.9); 2.5017 (383.65); 2.4982 (282.92); 2.3283 (2.31); 2.0733 (2.62); 1.9883 (1.97); 1.8712 (0.61); 1.7761 (11.28); 1.7311 (4.12); 1.6113 (1.99); 1.5966 (6.09); 1.5904 (5.32); 1.5777 (2.22); 1.2931 (0.88); 1.279 (1.92); 1.273 (2.06); 1.2578 (0.96); 1.2365 (1.31); 1.2229 (1.94); 1.2088 (4.32); 1.2025 (4.5); 1.1879 (1.67); 1.1747 (0.96); 1.1567 (0.93); 0.0078 (1.82); -0.0002 (58.33); - 0.0086 (1.83); -2.3925 (0.46); -2.4975 (0.45); -3.438 (0.46

Application 31, solvent: IDMSOI, spectrometer: 399.95 MHz 9.6271 (0.33); 9.486864 (1.04); 9.3652 (4.55); 7.6886 (0.76); 7.6822 (0.75); 7.586821 (0.72); 7.5605 (1.05); 7.4744 (2.86); 7.4687 (2.84); 7.4508 (0.45); 7.4243 (4.62); 7.4029 (5.04); 7.3666 (0.94); 7.362 (1.49); 7.3577 (0.73); 7.345 (4.29); 7.341 (2.48); 7.3269 (4.69); 7.3153 (1.34); 7.311 (2.53); 7.3074 (1.78); 7.3007 (0.69); 7.2937 (2.58); 7.2842 (0.59); 7.2752 (0.73); 7.2699 (0.96); 7.2509 (1.5); 7.2417 (3.98); 7.2377 (4.77); 7.2211 (3.59); 7.0343 (0.74); 7.0277 (0.66); 7.0153 (0.67); 6.96 (1.73); 6.9536 (1.69); 6.9387 (1.64); 6.9318 (1.6); 5.4626 (2.05); 5.4257 (2.49); 4.9216 (1.23); 4.9128 (2.37); 4.8762 (2.17); 4.0758 (0.37); 4.0556 (0.88); 4.0379 (2.56); 4.0201 (2.74); 4.0023 (0.88); 3.9667 (3.2); 3.953935 (0.34); 3.8996 (16); 3.3929 (0.35); 3.39332 (300.56); 3.3257 (628.51); 3.3027 (7.43); 2.6752 (1.18); 2.686706 (1.5); 2.6659 (1.01); 2.5407 (0.853; 2.524 (2.63); 2.5193 (3.68); 2.5058 (169.66); 2.5016 (233.25); 2.4977 (156.25); 2.3329 (1.14); 2.3282 (1.65); 2.3237 (1.1213); 1.078 (1.078) (11.36); 1.6066 (1.94); 1.5924 (4.57); 1.5856 (4.63); 1.5728 (2.04); 1.2823 (0.53); 1.2698 (0.96); 1.2621 (1.07); 1.2482 (0.71); 1.235 (1.61); 1.2698 (0.96); (1.99); 1.198 (3.98); 1.1921 (7.04); 1.1746 (6.85); 1.1567 (3.11); 0.1462 (0.36); 0.0081 (2); -0.0002 (76.87); -0.0085 (2.13); -0.1493 (0.33

Application 32, solvent: IDMSOI, spectrometer: 399.95 MHz 19.4883 (0.33); 14.4743 (0.34); 9.9628 (0.33); 9.4772 (1.71); 9.366 (4.51); 8.5874 (0.8); 8.5782 (0.78); 8.5563 (2.19); 8.547 (2.12); 7.8384 (1.13); 7.8194 (2.22); 7.8147 (2.2); 7.8004 (1.32); 7.7955 (1.32); 7.7145 (0.49); 7.686895 (0.9); 7.6743 (0.51); 7.6709 (0.55); 7.5658 (1.2); 7.5441 (1.65); 7.533533 (1.55); 7.5212 (3.6); 7.5155 (3.87); 7.4745 (3.75); 7.4531 (4.46); 7.4106 (3.5); 7.3909 (2.71); 7.3429 (1.51); 7.3315 (1.79); 7.3238 (1.72); 7.3124 (1.73); 7.2885 (0.58); 7.2779 (0.44); 7.2717 (2.25); 7.265 (2.21); 7.2499 (1.86); 7.2432 (1.77); 7.1046 (0.9); 7.084868 (0.86); 5.296 (1.4); 5.256 (3.53); 5.2123 (3.53); 5.1725 (1.5); 4.9686 (2.74); 4.1368 (5.32); 4.0557 (0.94); 4.0379 (2.86); 4.0202 (2.95); 3.9976 (16); 3.3915 (0.41); 3.3305 (304.35); 3.3279 (296.34); 3.3249 (391.32); 3.2506 (0.34); 2.6708 (1.53); 2.5409 (0.84); 2.5016 (246.17); 2.4386 (0.36); 2.4326 (0.43); 2.3282 (1.61); 2.0734 (1.6); 1.9885 (11.41); 1.9079 (0.43); 1.6004 (2.1); 1.5867 (5.4); 1.5798 (5.52); 1.5671 (2.28); 1.2692 (0.65); 1.2565 (1.56); 1.2491 (1.54)3; 1.235 (1.41); 1.2013 (1.93); 1.192 (5.11); 1.1816 (4.31); 1.1746 (6.69); 1.1672 1.83); 1.1569 (3.02); 0.0075 (2.36); -0.0002 (43.57); -1.8063 (0.33

Application 33, solvent: IDMSOI, spectrometer: 399.95 MHz 9.5775 (4.49); 9.5053 (0.45); 7.7786 (3.6); 7.768682 (0.92); 7.7572 (4.87); 7.7138 (0.34); 7.692 (0.35); 7.5946 (0.68); 7.573 (0.96); 4.0552 (0.63); 4.0374 (1.94); 4.0273 (2.07); 4.0163 (16); 4.002 (0.93); 3.4947 (0.62); 3.486821 (0.65); 3.3765 (615.2); 3.372 (488.62); 3.3684 (526.05); 3.3645 (546.77); 3.3625 (654.08); 3.359 (560.12); 3.2239 (0.35); 2.6782 (1.18); 2.6736 (1.67); 2.669 (1.25); 2.5438 (0.92); 2.527 (3); 2.5222 (4.56); 2.5136 (82.6); 2.5091 (180.41); 2.5045 (246.26); 2.5 (178.36); 2.4955 (86.07); 2.3358 (1.2); 2.339312 (1.65); 2.3267 (1.27); 2.2807 (1.71); 2.2634 (1.73); 2.2212 (0.46); 2.2023 (0.41); 2.0759 (1.71); 1.9902 (8.07); 1.6323 (1.61); 1.6181 (3.95); 1.6112 (4.4); 1.5979 (2.13); 1.3975 (0.64); 1.3544 (0.4); 1.2986 (2.04); 1.2849 (4.05); 1.2782 (4.47); 1.2636 (1.91); 1.2528 (0.8); 1.2356 (1.05); 1.1924 (2.24); 1.1746 (4.33); 1.1568 (2.15); 1.0046 (0.45); 0.9858 (0.8); 0.967 (0.39); 0.9035 4.02); 0.8858 (8.59); 0.8681 (3.9); 0.008 (0.47); -0.0002 (15.07); -0.0086 (0.55

Application 34, solvent: IDMSOI, spectrometer: 601.6 MHz 11.5357 (2.35); 9.5094 (2.93); 7.7744 (2.41); 7.7701 (2.69); 7.7094 (1.22); 7.7051 (1.07); 7.6949 (1.54); 7.6906 (1.44); 7.5923 (2.62); 7.5777 (2.13); 4.3468 (0.77); 4.3348 (2.43); 4.3228 (2.45); 4.393107 (0.79); 4.0465 (1.21); 4.0346 (3.71); 4.0228 (3.71); 4.011 (1.24); 3.3485 (39.29); 3.063 (1.4); 2.8638 (1.42); 2.5098 (6.24); 2.5069 (13.35); 2.5039 (18.23); 2.5009 (13.5); 2.498 (6.41); 1.991 (16); 1.6057 (1.04); 1.5963 (2.46); 1.5918 (2.7); 1.5829 (1.07); 1.4232 (3.53); 1.4112 (7.51); 1.3991 (3.52); 1.3831 (0.35); 1.371 (0.73); 1.359 (0.33); 1.2704 (1.14); 1.2612 (2.43); 1.2568 (2.67); 1.2472 (1); 1.186869 4.33); 1.175 (8.76); 1.1632 (4.27); -0.0002 (1.62

Application 35, solvent: IDMSOI, spectrometer: 399.95 MHz 11.5005 (4.87); 9.4951 (6.27); 7.7618 (4.81); 7.7554 (5.95); 7.7144 (2.63); 7.7078 (2); 7.6925 (3.37); 7.686 (2.85); 7.5904 (5.35); 7.5686 (3.92); 4.2725 (3.11); 4.2554 (6.27); 4.2381 (3.15); 4.0382 (0.36); 4.0188 (0.33); 3.486841 (0.32); 3.4614 (0.46); 3.4443 (0.55); 3.4137 (0.86); 3.3433 (1492.06); 3.2822 (3.03); 3.25 (1.84); 3.2136 (1.16); 3.1836 (0.68); 3.1568 (0.48); 3.0604 (1.58); 2.8553 (1.58); 2.6765 (0.88); 2.6715 (1.15); 2.6668 (0.89); 2.5808 (0.37); 2.5419 (0.94); 2.5068 (140.47); 2.5027 (192.83); 2.4986 (142.05); 2.4395 (1.46); 2.4062 (0.88); 2.4024 (0.84); 2.3507 (0.48); 2.3295 (1.39); 2.3251 (1.13); 2.3016 (0.38); 2.0748 (2.08); 1.9892 (1.51); 1.8724 (0.6); 1.8543 (2.3); 1.8363 (4.51); 1.8184 (4.61); 1.8002 (2.47); 1.7815 (0.63); 1.6082 (2.21); 1.5942 (5.23); 1.5868 (5.61); 1.5738 (2.55); 1.5334 (0.32); 1.3974 (9.15); 1.2748 (2.5); 1.2617 (5.29); 1.2545 (5.68); 1.24 (2.34); 1.1923 (0.45); 1.1741 (0.77); 1.1568 (0.42); 0.8614 (7.69); 0.843931 (16); 0.8244 (7.18); -0.0002 (12.56); -0.0087 (0.62

Application 36, solvent: IDMSOI, spectrometer: 601.6 MHz 11.4548 (1.5); 9.3583 (1.27); 7.9479 (0.56); 7.9434 (0.64); 7.9378 (0.61); 7.9332 (0.58); 7.7878 (0.37); 7.786856 (0.39); 7.786807 (0.35); 7.7778 (0.36); 7.7728 (0.41); 7.771 (0.4); 7.4149 (0.55); 7.3992 (0.89); 7.3837 (0.52); 4.2745 (0.87); 4.2629 (1.71); 4.2513 (0.87); 4.0461 (1.23); 4.0343 (3.73); 4.0224 (3.73); 4.0106 (1.24); 3.3508 (5.32); 3.0615 (0.46); 2.857 (0.46); 2.5216 (0.38); 2.5067 (18.22); 2.5038 (24.1); 2.5008 (17.69); 1.9909 (16); 1.8508 (0.62); 1.8388 (1.21); 1.8269 (1.23); 1.8149 (0.65); 1.5953 (0.63); 1.5859 (1.53); 1.5813 (1.8); 1.5724 (0.68); 1.2932 (0.72); 1.2841 (1.56); 1.2796 (1.68); 1.2702 (0.7); 1.1866 (4.25); 1.1747 (8.49); 1.1629 (4.18); 0.9297 (0.46); 0.8596 (1.94); 0.8473 (4.1); 0.835 1.9); 0.8263 (0.36); -0.0002 (1.87

Application 37, solvent: IDMSOI, spectrometer: 399.95 MHz 11.4582 (4.4); 9.3437 (3.47); 7.9546 (1.99); 7.9477 (2.21); 7.9391 (2.06); 7.935323 (2.22); 7.7969 (1.11); 7.7896 (1.15); 7.7858 (1.31); 7.7786 (1.09); 7.7744 (1.19); 7.7674 (1.35); 7.7633 (1.35); 7.7565 (1.05); 7.4195 (2.16); 7.3953 (2.98); 7.3726 (1.97); 4.4209 (0.48); 4.402 (0.49); 4.3576 (1.39); 4.335397 (4.42); 4.3215 (4.47); 4.303931 (1.4); 4.2264 (0.44); 4.209 (0.72); 4.1911 (0.99); 4.1728 (0.68); 4.0554 (1.12); 4.0376 (3.61); 4.0198 (3.61); 4.002 (1.17); 3.4598 (0.4); 3.3366 (26.64); 3.2408 (0.63); 3.2327 (0.6); 3.18 (0.49); 3.0617 (7.35); 2.9068 (0.33); 2.862 (7.44); 2.6758 (0.84); 2.6713 (1.17); 2.6666 (0.87); 2.5416 (0.6); 2.5245 (2.07); 2.5199 (2.85); 2.5063 (123.98); 2.5022 (170.52); 2.4985 (114.01); 2.3384 (0.38); 2.3333 (0.8); 2.3286 (1.21); 2.3245 (0.85); 2.3194 (0.49); 2.0755 (0.47); 1.9893 (16); 1.9091 (0.6); 1.5982 (1.91); 1.5841 (4.44); 1.5769 (4.72); 1.5638 (2.26); 1.4339 (6.76); 1.4158 (15.95); 1.3976 (7.06); 1.3891 (2.15); 1.3757 (2.45); 1.371 (4.02); 1.3576 (1.14); 1.3528 (1.86); 1.2979 (2.59); 1.2842 (4.49); 1.2773 (4.85); 1.2627 (2.22); 1.2354 (0.95); 1.1923 (4.5); 1.1745 (8.88); 1.1567 (4.35); 0.8883 (0.35); 0.008 (0.92); -0.0002 (35.96); -0.0085 (1.05

Application 38, solvent: IDMSOI, spectrometer: 601.6 MHz 9.5496 (0.57); 9.4141 (0.99); 7.953531 (2.11); 7.6736 (0.9); 7.6699 (0.6); 7.6588 (0.63); 7.5771 (0.34); 7.5534 (0.98); 7.5391 (1.1); 7.433 (0.87); 7.4286 (0.92); 7.2912 (0.53); 7.2868 (0.49); 7.2769 (0.48); 7.2725 (0.45); 4.3763 (0.46); 4.3643 (0.47); 4.2607 (0.37); 4.1747 (0.32); 4.1628 (0.38); 3.4447 (5.41); 3.3584 (170.61); 3.335 (1.41); 3.2387 (2.83); 2.8911 (16); 2.7312 (13.04); 2.7307 (12.77); 2.5251 (0.36); 2.522 (0.46); 2.5189 (0.48); 2.5099 (12.87); 2.507 (27.63); 2.504 (37.72); 2.501 (27.87); 2.4981 (13.11); 1.6046 (0.84); 1.6005 (0.7); 1.5953 (0.94); 1.5911 (1.16); 1.5824 (0.42); 1.4525 (0.74); 1.4405 (1.57); 1.4285 (0.74); 1.308 (1.26); 1.296 (2.69); 1.2908 (0.39); 1.284 (1.46); 1.2771 (0.59); 1.1964 (0.45); 1.1876 (0.87); 1.1835 (0.88); 1.1744 (0.48); -0.0002 (5.92

Application 39, solvent: IDMSOI, spectrometer: 399.95 MHz 16.4832 (0.33); 15.8688 (0.33); 13.2954 (0.33); 9.6257 (0.34); 9.6097 (2.28); 9.4715 (4.25); 9.4357 (0.37); 9.3286 (0.34); 8.0115 (1.98); 8.0058 (2.14); 7.6392 (4.36); 7.633935 (3.82); 7.6013 (0.4); 7.5949 (0.44); 7.5777 (0.47); 7.5615 (0.48); 7.5253 (0.37); 7.4896 (3.22); 7.486834 (3.02); 7.4395 (0.43); 7.4325 (0.57); 7.4255 (0.52); 7.4196 (0.37); 5.7522 (0.33); 4.1774 (0.4); 4.1601 (0.99); 4.1421 (1.31); 41253 (1.47); 4.1073 (1.28); 4.0847 (8.62); 4.0554 (1.29); 4.0376 (3.86); 4.0199 (3.78); 4.0022 (1.25); 3.9064 (0.38); 3.8793 (1.92); 3.8664 (14.52); 3.8554 (1.87); 3.8367 (0.71); 3.8182 (1.21); 3.8004 (1.64); 3.786833 (1.43); 3.7657 (1.14); 3.7471 (0.43); 3.7013 (0.51); 3.6822 (0.73); 3.6642 (0.9); 3.6454 (1); 3.6338 (0.83); 3.6158 (0.91); 3.5968 (0.64); 3.5781 (0.38); 3.4622 (0.34); 3.4401 (0.39); 3.4079 (0.75); 3.3466 (768.76); 3.3431 (1758.18); 3.3199 (5.3); 3.2876 (0.84); 3.2746 (0.59); 3.2684 (0.52); 3.2291 (0.35); 3.2188 (0.44); 2.6767 (1.39); 2.6717 (1.92); 2.6678 (1.4); 2.5418 (0.89); 2.5252 (3.39); 2.5111 (113.97); 2.5071 (219.12); 2.5029 (302.49); 2.4987 (211.86); 2.4946 (105.8); 2.4557 (0.43); 2.339342 (1.35); 2.3295 (1.8); 2.3249 (1.43); 2.075 (2.09); 1.9893 (16); 1.6178 (2.02); 1.6037 (6.07); 1.5977 (5.35); 1.586842 (2.19); 1.5755 (0.39); 1.3835 (0.33); 1.3449 (0.36); 1.393127 (1.03); 1.298 (2.27); 1.2915 (2.11); 1.2761 (0.89); 1.2588 (0.57); 1.2327 (3.01); 1.2191 (4.19); 1.2121 (4.3); 1.1979 (1.6); 1.1924 (4.68); 1.1746 (8.79); 1.1567 (8.3); 1.1383 (9.27); 1.1204 (4.08); 1.0992 (0.35); 0.9885 (0.33); 0.9703 2.29); 0.9523 (4.58); 0.9345 (2.19); -0.0002 (11.63); -0.0088 (0.43); -3.0168 (0.32

Application 40, solvent: IDMSOI, spectrometer: 399.95 MHz 11.491 (2.41); 7.8981 (2.63); 7.8918 (2.76); 7.7092 (1.29); 7.7028 (1.18); 7.6873 (1.79); 7.686809 (1.74); 7.5849 (3.2); 7.563 (2.31); 4.056 (0.73); 4.0381 (2.56); 4.0288 (11.26); 4.0205 (2.67); 4.0026 (0.76); 3.3518 (0.45); 3.3286 (152.33); 2.5244 (1.09); 2.5195 (1.69); 2.5109 (19.1); 2.5065 (38.19); 2.502 (49.79); 2.4974 (35.73); 2.493 (17.31); 2.3955 (16); 2.3286 (0.34); 2.074 (0.42); 1.9888 (9.22); 1.8766 (1.77); 1.6065 (0.84); 1.1926 (2.46); 1.1748 (4.87); 1.157 (2.4); -0.0002 (5.14 bo

Application 41, solvent: IDMSOI, spectrometer: 601.6 MHz 9.4121 (0.42); 7.9528 (1.18); 7.7388 (0.36); 7.7028 (0.82); 7.6882 (1.07); 7.674 (0.37); 7.6583 (0.38); 7.6479 (0.99); 7.6438 (1.12); 7.6126 (1.11); 7.5995 (1.46); 7.5769 (0.36); 7.5533 (0.48); 7.5395 (0.48); 7.433 (0.5); 7.4291 (0.53); 7.3221 (0.64); 7.2903 (0.44); 7.2761 (0.33); 7.2716 (0.34); 4.3716 (1.39); 4.3595 (1.67); 4.272 (0.39); 4.2601 (0.39); 4.2481 (0.36); 4.1277 (0.42); 4.1191 (0.42); 4.0334 (0.56); 4.0216 (0.56); 3.5061 (0.42); 3.4808 (1.12); 3.4549 (16); 3.444 (2.94); 3.4284 (0.6); 3.3956 (1.34); 3.3758 (5.24); 3.3517 (4904.54); 3.3282 (80.11); 3.2755 (1.57); 3.2474 (4.78); 3.2383 (1.31); 3.1704 (1.74); 3.1617 (1.71); 3.1108 (1.82); 3.0743 (1.14); 2.8906 (8.65); 2.8645 (4.58); 2.7306 (7.07); 2.618 (10.41); 2.615 (14.06); 2.6121 (10.4); 2.5428 (5.84); 2.5243 (20.27); 2.5213 (25.42); 2.5182 (25.36); 2.5091 (738.32); 2.5062 (1554.79); 2.5033 (2093.86); 2.5003 (1556.28); 2.4974 (750.49); 2.3904 (9.64); 2.3874 (13.16); 2.3845 (9.61); 2.283 (0.4); 2.0787 (15.29); 1.9906 (2.25); 1.6777 (3.23); 1.6044 (0.51); 1.591 (0.77); 1.582 (0.49); 1.5066 (0.63); 1.4948 (0.86); 1.4825 (0.67); 1.4514 (2.04); 1.4394 (4.05); 1.4273 (2.94); 1.415 (1.05); 1.3496 (2.36); 1.3072 (1.28); 1.2954 (1.78); 1.2833 (1.18); 1.2666 (0.69); 1.2576 (1.03); 1.2338 (6.68); 1.1951 (0.48); 1.1859 (1.2); 1.174 (1.49); 1.1622 (0.72); 1.0541 (0.42); 0.8646 (0.43); 0.8535 (1.03); 0.8416 (0.52); 0.0965 (1.89); 0.0052 (14.67); -0.0002 473.67); -0.0057 (19.93); -0.1 (1.92

Application 42, solvent: IDMSOI, spectrometer: 601.6 MHz 11.0933 (3.12); 10.6126 (0.51); 9.5132 (3.58); 9.5027 (0.8); 7.8641 (2.73); 7.86 (2.86); 7.8428 (1.09); 7.839 (0.51); 7.8313 (0.4); 7.7552 (1.31); 7.751 (1.2); 7.7406 (1.56); 7.7365 (1.44); 7.5785 (3.5); 7.564 (2.35); 7.5578 (0.51); 7.5418 (0.41); 4.1945 (2.61); 4.0334 (0.76); 4.0215 (0.81); 4.0064 (12.33); 3.3813 (1.49); 3.3561 (1038.24); 3.3325 (10.5); 2.6153 (1.84); 2.543 (0.72); 2.5245 (2.78); 2.5214 (3.59); 2.5181 (4.4); 2.5063 (218.81); 2.5036 (275.25); 2.3877 (1.67); 2.2932 (0.59); 2.2827 (16); 2.0785 (0.51); 1.9907 (3.1); 1.6109 (1.37); 1.6016 (3.69); 1.5971 (3.87); 1.586881 (1.44); 1.2646 (1.41); 1.2554 (3.39); 1.2511 (3.52); 1.2413 (1.86); 1.2344 (0.88); 1.1859 (0.82); 1.1741 (1.59); 1.1622 0.81); 0.0049 (1.62); -0.0002 (30.57

Application 43, solvent: IDMSOI, spectrometer: 601.6 MHz 9.5611 (2.61); 9.4204 (5.99); 7.6917 (2.08); 7.6775 (2.5); 7.644 (2.35); 7.6398 (2.43); 7.5687 (5.27); 7.5544 (5.96); 7.5008 (1.35); 7.4967 (1.29); 7.4867 (1.16); 7.4825 (1.15); 7.4199 (4.23); 7.4158 (4.42); 7.2921 (2.65); 7.288 (2.5); 7.2779 (2.46); 7.2736 (2.33); 4.3914 (0.77); 4.3788 (2.21); 4.367 (2.26); 4.3549 (0.78); 4.268 (0.45); 4.2567 (1.31); 4.2449 (1.84); 42335 (2.3); 42217 (1.95); 4.21 (0.64); 4.1658 (0.64); 4.1541 (1.99); 4.1423 (2.5); 4.1343 (1.96); 4.1311 (2.19); 4.1224 (2.3); 4.1193 (1.88); 4.1114 (2.32); 4.0996 (1.8); 4.0878 (0.56); 4.0334 (0.37); 4.0216 (0.36); 3.7795 (0.53); 3.7678 (1.63); 3.7559 (2.07); 3.7448 (1.99); 3.7328 (1.56); 3.7214 (0.53); 3.6918 (0.56); 3.68 (0.78); 3.6676 (0.94); 3.6558 (0.78); 3.5796 (0.83); 3.5678 (1); 3.5556 (0.85); 3.5436 (0.6); 3.4046 (0.45); 3.3945 (1.21); 3.3858 (1.16); 3.3796 (1.18); 3.3518 (1984.37); 3.3279 (16.06); 3.3028 (0.46); 3.1702 (0.33); 3.1616 (0.43); 2.6179 (4.37); 2.6151 (5.71); 2.6123 (4.23); 2.5427 (2.81); 2.5332 (0.94); 2.5242 (9.59); 25211 (13.27); 2.5179 (16.58); 2.5062 (657.61); 2.5033 (846.44); 2.5005 (615.2); 2.4784 (2.21); 2.3903 (3.99); 2.3875 (5.24); 2.3847 (3.83); 2.0787 (4.37); 1.9906 (1.25); 1.6177 (1.12); 1.6056 (4.24); 1.5967 (6.28); 1.5925 (6.54); 1.5838 (2.53); 1.4508 (3.21); 1.4388 (6.55); 1.4268 (3.06); 1.306 (7.37); 1.2941 (16); 1.282 (9.65); 1.2721 (1.16); 1.2576 (0.69); 1.2338 (3.09); 1.2054 (2.8); 1.1965 (5.73); 1.1922 (5.97); 1.183 (2.39); 1.1741 (0.91); 1.1621 (0.47); 1.1436 (6.79); 1.1317 (13.97); 1.1198 (6.51); 0.9438 (2.6); 0.932 (5.36); 0.9202 (2.47); 0.8535 (0.4); 0.0967 (0.49); 0.005 (5.69); -0.0002 (104.53); - 0.0999 (0.47

Application 44, solvent: IDMSOI, spectrometer: 601.6 MHz 9.4685 (3.13); 7.6186 (2.15); 7.6043 (2.37); 7.5156 (2.09); 7.5118 (2.18); 7.3065 (1.24); 7.3024 (1.24); 7.2923 (1.16); 7.2882 (1.12); 5.2573 (1.78); 5.2279 (2.2); 4.9892 (2.11); 4.9598 (1.74); 4.0648 (0.9); 4.0453 (1.36); 4.033935 (3.87); 4.0217 (3.86); 4.0098 (1.32); 3.9354 (10.54); 3.4336 (0.7); 3.3766 (1.21); 3.352 (365.17); 3.3252 (0.47); 2.6151 (0.96); 2.5429 (0.42); 2.5034 (150.98); 2.3876 (0.93); 1.9907 (16); 1.6188 (1.49); 1.6097 (3.52); 1.6054 (3.55); 1.5965 (1.28); 1.2734 (0.4); 1.2338 (0.67); 1.217 (1.28); 1.2079 (2.97); 1.2038 (3.11); 1.1942 (1.13); 1.186 (4.37); 1.1742 (8.34); 1.1623 (4.17); - 0.0002 (1.27

Application 45, solvent: IDMSOI, spectrometer: 399.95 MHz 11.5629 (3.17); 9.5197 (3.89); 7.8939 (0.68); 7.8145 (2.97); 7.8081 (3.34); 7.6813 (1.42); 7.675 (1.32); 7.6594 (2.05); 7.653 (2.01); 7.5849 (4.03); 7.563 (2.7); 7.5353 (0.32); 5.7625 (0.52); 4.1942 (1); 4.1104 (12.73); 4.0549 (0.57); 4.0371 (1.62); 4.0193 (1.67); 4.0016 (0.65); 3.3488 (381.8); 3.3413 (634.34); 3.0337 (16); 2.681 (0.92); 2.6766 (1.94); 2.672 (2.7); 2.6675 (1.97); 2.5421 (1.6); 2.5254 (4.95); 2.5207 (7.26); 2.512 (132.84); 2.5075 (285.73); 2.503 (383.95); 2.4984 (271.1); 2.4939 (125.41); 2.3389 (0.83); 2.3343 (1.83); 2.3297 (2.55); 2.3251 (1.84); 2.0772 (0.62); 1.99 (7.2); 1.612 (1.36); 1.5977 (3.37); 1.5909 (3.47); 1.5778 (1.53); 1.2731 (1.73); 1.2596 (3.49); 1.2529 (3.76); 1.2378 (2.87); 1.1921 (1.91); 1.1742 (3.78); 1.1565 (1.84); 0.8539 (0.37); 0.008 (1.19); -0.0002 (35.07); - 0.0077 (1.04

Application 45, solvent: IDMSOI, spectrometer: 399.95 MHz 11.5617 (2.61); 9.5199 (2.8); 7.8135 (2.59); 7.8072 (2.92); 7.6806 (1); 7.6741 (0.94); 7.6586 (1.53); 7.656522 (1.56); 7.5846 (2.73); 7.5627 (1.8); 4.1102 (12.24); 4.0369 (0.87); 4.0191 (0.88); 4.0016 (0.61); 3.3499 (1797.52); 3.2245 (0.46); 3.033 (16); 2.686813 (0.63); 2.6767 (1.35); 2.6721 (1.89); 2.6675 (1.39); 2.6629 (0.67); 2.5424 (1.08); 2.5255 (3.44); 2.5208 (5.1); 2.5121 (94.77); 2.5076 (206.74); 2.503 (279.76); 2.4984 (197.63); 2.4939 (91.37); 2.3389 (0.58); 2.3343 (1.29); 2.3297 (1.81); 2.3252 (1.91); 2.0765 (2.83); 1.9898 (4.26); 1.6115 (1.29); 1.5972 (2.98); 1.5904 (3.18); 1.5772 (1.42); 1.273 (1.66); 1.2592 (3.23); 1.2526 (3.51); 1.2379 (1.98); 1.192 (1.13); 1.1742 (2.25); 1.1564 (1.08); -0.0002 (8.57

Application 46, solvent: IDMSOI, spectrometer: 399.95 MHz 9.5373 (0.47); 9.3983 (0.81); 7.7053 (0.41); 7.6838 (0.63); 7.6757 (0.42); 7.6635 (0.45); 7.6546 (0.75); 7.6313 (0.77); 7.6092 (1.26); 7.5886 (1.33); 7.5792 (0.79); 7.5486 (0.9); 7.527 (0.97); 7.4347 (0.79); 7.4282 (0.89); 7.3883 (0.47); 7.3078 (1.04); 7.2891 (0.66); 7.2824 (0.56); 7.2677 (0.47); 7.2612 (0.45); 4.2924 (1.02); 4.2751 (0.9); 4.182 (0.47); 4.1649 (0.51); 4.1476 (0.56); 4.1292 (0.35); 4.0547 (1.37); 4.0369 (3.7); 4.0191 (3.74); 4.0013 (1.31); 3.4557 (10.09); 3.4453 (5.02); 3.3427 (771.28); 3.319 (13.1); 3.2679 (1.37); 3.2419 (3.06); 3.2325 (2.72); 3.1112 (1.16); 3.072 (0.85); 2.8904 (0.43); 2.8646 (2.78); 2.739312 (0.35); 2.6764 (1.44); 2.6718 (2); 2.6673 (1.53); 2.5422 (1.53); 2.5253 (3.59); 2.5205 (5.22); 2.5117 (95.58); 2.5073 (207.41); 2.5028 (281.65); 2.4982 (204.86); 2.4938 (99.47); 2.334 (1.35); 2.3295 (1.9); 2.325 (1.43); 2.0769 (2.16); 1.9899 (16); 1.9015 (0.53); 1.8832 (1); 1.8655 (1.18); 1.847 (0.97); 1.8267 (0.75); 1.8103 (0.56); 1.7924 (0.52); 1.7738 (0.52); 1.6767 (2.49); 1.6439 (0.6); 1.6192 (0.38); 1.5969 (1.32); 1.5899 (1.04); 1.5768 (0.52); 1.4012 (0.6); 1.2967 (0.71); 1.2823 (0.75); 1.2755 (0.81); 1.258 (0.71); 1.2347 (1.66); 1.2004 (0.58); 1.192 (4.72); 1.1743 (9.08); 1.1564 (4.38); 0.8945 (1.45); 0.876 (3.76); 0.8567 (3.53); 0.8335 (2.44); 0.8148 (2.63); 0.7962 (1.13); 0.146 0.39); 0.008 (2.78); -0.0002 (90.84); -0.0085 (3.33); -0.1499 (0.34

Application 47, solvent: IDMSOI, spectrometer: 601.6 MHz 7.686521 (0.53); 7.4488 (0.87); 7.4092 (0.79); 7.3946 (0.85); 7.3798 (0.87); 4.3079 (0.35); 4.2962 (0.64); 4.2842 (0.81); 4.2717 (0.82); 4.2604 (0.93); 4.2489 (1.03); 4.2369 (0.57); 4.1612 (0.58); 4.1506 (0.59); 4.1386 (0.49); 4.127 (0.54); 4.1149 (0.59); 4.1037 (0.33); 4.0456 (0.57); 4.0338 (1.71); 4.022 (1.73); 4.0101 (0.58); 3.4532 (16); 3.4036 (1.29); 3.3797 (0.39); 3.3536 (287.87); 3.33 (4.06); 3.2402 (1.45); 3.1042 (0.53); 3.095 (0.47); 3.063931 (0.57); 2.9405 (0.67); 2.6832 (2.06); 2.6186 (0.56); 2.6157 (0.74); 2.6128 (0.54); 2.5249 (1.23); 2.5218 (1.83); 2.5069 (84.85); 2.504 (111.28); 2.501 (80.94); 2.391 (0.55); 2.3881 (0.73); 2.3852 (0.53); 1.9909 (7.37); 1.8792 (0.58); 1.8669 (0.68); 1.8549 (0.61); 1.8371 (0.59); 1.7449 (0.46); 1.7341 (0.59); 1.7232 (0.61); 1.7109 (0.61); 1.6979 (0.68); 1.686 (0.86); 1.6637 (1.33); 1.4754 (0.37); 1.3882 (0.95); 1.2578 (0.37); 1.2343 (1.25); 1.1862 (2.13); 1.1744 (4.02); 1.1625 (2.03); 0.8889 (1.11); 0.8766 (2.26); 0.8638 (2.34); 0.8493 (3.1); 0.6607 (0.53); 0.6484 (1.06); 0.6361 (0.51); 0.0051 (1.29); -0.0002 (25.89); -0.0056 (0.98

Application 48, solvent: IDMSOI, spectrometer: 601.6 MHz 7.686625 (0.59); 7.6566 (0.58); 7.6531 (0.62); 7.441 (0.93); 7.4125 (0.97); 7.3978 (1.05); 4.3751 (0.97); 4.3634 (1.3); 4.3523 (1.07); 4.3412 (1.13); 4.3294 (0.96); 4.3177 (0.36); 4.2724 (0.53); 4.0335 (0.92); 4.0217 (0.91); 3.4526 (16); 3.3768 (0.53); 3.3522 (580.58); 3.3286 (7.62); 3.2446 (1.32); 3.1036 (0.51); 3.0656 (0.51); 2.9399 (0.7); 2.686805 (2.05); 2.6182 (1.09); 2.6153 (1.49); 2.6123 (1.1); 2.543 (0.62); 2.5245 (2.25); 2.5215 (3.05); 2.5183 (3.8); 2.5094 (79.16); 2.5065 (164.86); 2.5035 (221.76); 2.5005 (162.52); 2.4977 (78.12); 2.3906 (1.05); 2.3877 (1.43); 2.3847 (1.05); 2.0789 (0.5); 1.9907 (3.97); 1.9066 (0.38); 1.6608 (1.13); 1.4749 (0.38); 1.4506 (0.98); 1.4387 (1.81); 1.4266 (1.1); 1.3791 (0.88); 1.3467 (2.94); 1.2977 (0.44); 1.2577 (0.56); 1.2337 (1.42); 1.186 (1.28); 1.1742 (2.31); 11623 1.19); 0.0052 (2.55); -0.0002 (61.56); -0.0057 (2.57

Application 49, solvent: IDMSOI, spectrometer: 399.95 MHz 11.3656 (3.86); 9.5142 (4.4); 7.7755 (3.59); 7.7692 (3.97); 7.6847 (1.75); 7.6783 (1.49); 7.6628 (2.52); 7.6564 (2.33); 7.5817 (4.49); 7.5599 (3.05); 4.0562 (1.15); 4.0384 (3.4); 4.0206 (3.6); 4.0034 (16); 3.3453 (94.9); 3.3448 (94.73); 3.3197 (17.97); 2.5245 (0.51); 2.511 (7.72); 2.5068 (14.99); 2.5023 (19.26); 2.4978 (13.84); 2.4937 (6.76); 2.0729 (0.59); 1.9887 (13.71); 1.6091 (1.56); 1.5949 (3.86); 1.588 (4.03); 1.5747 (1.73); 1.277 (1.86); 1.2635 (3.82); 1.2568 (4.07); 1.2422 (1.5); 1.1928 (3.82); 1.1749 (7.49); 1.1572 (3.7

Application 50, solvent: IDMSOI, spectrometer: 601.6 MHz 9.5618 (2.56); 9.4177 (6.18); 7.9529 (0.98); 7.6923 (2.28); 7.6781 (2.69); 7.635 (2.45); 7.6308 (2.6); 7.5617 (5.97); 7.5475 (6.73); 7.5004 (1.4); 7.4963 (1.31); 7.486863 (1.23); 7.482 (1.22); 7.4233 (4.05); 7.4191 (4.25); 7.2874 (2.63); 7.283 (2.53); 7.2731 (2.42); 7.265688 (2.31); 4.3107 (0.81); 4.3036 (0.87); 4.2993 (1.52); 4.2921 (1.53); 4.2806 (0.81); 4.1677 (0.49); 4.1596 (1.05); 4.1559 (1.81); 4.1474 (2.05); 4.144 (2.45); 4.1362 (2.11); 4.1329 (2.74); 4.1249 (2.63); 4.1211 (2.27); 4.1128 (1.37); 4.0421 (1.16); 4.0323 (1.53); 4.0297 (1.5); 4.0196 (1.98); 4.0097 (1.08); 4.0068 (1.07); 3.9968 (0.83); 3.7605 (0.48); 3.7486 (1.68); 3.7369 (2.16); 3.7256 (2.07); 3.7139 (1.61); 3.7018 (0.54); 3.6876 (0.53); 3.6756 (0.76); 3.6634 (0.93); 3.6514 (0.75); 3.5736 (0.78); 3.5616 (0.93); 3.5493 (0.81); 3.5373 (0.58); 3.4009 (0.71); 3.3887 (0.8); 3.3806 (1.37); 3.3578 (1317.4); 3.334 (5.83); 2.8908 (7.36); 2.7308 (5.98); 2.6185 (1.57); 2.6155 (2.16); 2.6126 (1.59); 2.5433 (0.92); 2.5248 (3.01); 2.5217 (4.1); 2.5186 (4.76); 2.5095 (118.16); 2.5067 (245.74); 2.5038 (330.23); 2.5009 (240.75); 2.4981 (114.58); 2.3909 (1.49); 2.3879 (2.06); 2.385 (1.48); 2.078687 (0.93); 1.886893 (1); 1.8773 (2.04); 1.8652 (2.07); 1.8532 (1.07); 1.8217 (0.59); 1.8094 (1.15); 1.7977 (1.5); 1.7863 (1.743; 1.7743 (1.53); 1.7621 (0.74); 1.6799 (0.65); 1.6676 (1.17); 1.6574 (1.68); 1.645 (1.65); 1.6348 (1.13); 1.6225 (0.67); 1.6179 (1.604); (4.94); 1.6039 (3.6); 1.5991 (6.24); 1.5947 (7.45); 1.5859 (2.64); 1.2954 (1.19); 1.2863 (2.43); 1.2819 (2.67); 12724 (1); 1.2578 (0.42); 1.2335 (1.57); 1.2037 (2.86); 1.1947 (5.93); 1.1903 (6.34); 1.181 (2.45); 1.1407 (7.11); 1.1288 (14.87); 1.1168 (6.89); 0.9415 (2.6); 0.9297 (5.469); 0.9 (2.57); 0.8865 (3.17); 0.8743 (6.67); 0.862 (3.13); 0.8535 (0.38); 0.8172 (7.63); 0.8049 (16); 0.7926 (7.21); 0.0051 (1.34); -0.0002 32.06); -0.0057 (1.19

Application 51, solvent: IDMSOI, spectrometer: 601.6 MHz 11.2435 (1); 9.3497 (0.74); 7.9531 (0.39); 7.7736 (0.6); 7.7601 (0.7); 7.7304 (2.91); 7.7161 (3.91); 7.686522 (3.79); 7.6386 (3.74); 7.6244 (3.53); 7.5889 (2.65); 7.5753 (2.41); 7.5207 (1.21); 7.4121 (11.62); 7.4027 (3.64); 7.3862 (2.56); 7.3118 (2.15); 7.2988 (1.8); 7.2009 (0.39); 6.8169 (0.48); 4.3007 (3.14); 4.2901 (3.3); 4.2794 (2.58); 4.2566 (2.26); 4.2028 (1.63); 4.1284 (3.82); 4.1178 (3.61); 44107 (3.02); 4.0674 (1.32); 4.055 (1.55); 4.0456 (2.7); 4.0338 (4.82); 4.022 (4.4); 4.0102 (1.78); 3.9587 (1.64); 3.947 (2.06); 3.9353 (1.89); 3.9165 (1.96); 3.9041 (2.3); 3.8933 (1.94); 3.8468 (1.72); 3.7093 (1.04); 3.6044 (0.96); 3.3585 (2804.89); 3.3349 (16.31); 3.2711 (0.92); 3.2466 (0.88); 3.1423 (0.68); 3.0944 (0.54); 3.061 (1.47); 3.0465 (1.27); 2.9693 (1.33); 2.8912 (2.99); 2.8563 (1.82); 2.8399 (3.68); 2.8293 (3.66); 2.7312 (2.47); 2.6188 (3.62); 2.616 (4.79); 2.6132 (3.59); 2.5436 (1.95); 2.525 (9.26); 2.522 (12.69); 2.5186 (16.24); 2.507 (555.84); 2.5043 (726.37); 2.5015 (536.53); 2.3912 (3.62); 2.3884 (4.75); 2.3856 (3.53); 2.2958 (0.37); 2.2837 (0.81); 2.2716 (0.33); 2.0789 (2.13); 1.991 (15.17); 1.8862 (1.72); 1.8744 (3.51); 1.8624 (4.2); 1.8509 (3.63); 1.8425 (3.66); 1.8307 (3.67); 1.8188 (3.58); 1.8066 (2.89); 1.794 (2.27); 1.7812 (2.03); 1.7642 (2.22); 1.7173 (14.52); 1.6892 (3.36); 1.6419 (1.13); 1.5709 (1.75); 1.5668 (1.84); 1.5023 (3.27); 1.4837 (3.07); 1.374 (3.95); 1.3622 (2.97); 1.3502 (2.21); 1.333534 (3.83); 1.3217 (5.49); 1.3103 (4.13); 1.2978 (3.26); 1.2679 (4.55); 1.2579 (5.13); 1.2343 (9.67); 1.1974 (3.99); 1.1862 (10.63); 1.1743 (14.27); 1.1624 (12.11); 1.1558 (13.88); 1.1412 (16); 1.1295 (8.23); 1.1049 (6.61); 1.0708 (6); 1.0599 (8.58); 0.9401 (3.69); 0.9284 (5.1); 0.9172 (2.68); 0.8835 (5.11); 0.8713 (10.54); 0.865 (6.44); 0.8588 (10.32); 0.8536 (8.8); 0.845 (12.86); 0.8317 (12.07); 0.78 (1.98); 0.7676 (0.91); 0.0966 (0.62); 0.005 (6.46); -0.0002 (127.14); -0.0055 (5.46); -0.1 (0.6

Application 52, solvent: IDMSOI, spectrometer: 399.95 MHz 9.4063 (0.33); 7.7318 (0.72); 7.7103 (0.89); 7.6897 (0.37); 7.6725 (0.36); 7.6593 (1.1); 7.6531 (1.26); 7.6406 (1.06); 7.6247 (0.89); 7.5947 (0.61); 7.5698 (0.76); 7.5483 (0.56); 7.5048 (0.39); 7.4401 (0.74); 7.4106 (1.09); 7.3918 (1.37); 7.2958 (0.47); 7.2895 (0.56); 7.2747 (0.49); 7.2686 (0.49); 4.4001 (0.35); 4.3823 (1.01); 4.3643 (1.22); 4.2654 (0.77); 4.2473 (0.94); 4.2311 (0.91); 4.2129 (0.73); 4.1602 (0.44); 4.147 (0.55); 4.1419 (0.6); 4.1332 (0.55); 4.1246 (0.64); 4.1084 (0.36); 4.055 (1.34); 4.0461 (0.4); 4.0372 (3.72); 4.0282 (0.46); 4.0194 (3.81); 4.0016 (1.44); 3.9349 (0.82); 3.9199 (0.86); 3.6846 (0.33); 3.6661 (0.36); 3.6171 (0.37); 3.5995 (0.37); 3.5078 (0.35); 3.393637 (1.04); 3.3424 (804.32); 3.3186 (9.85); 3.2893 (0.5); 3.2722 (0.6); 3.2519 (0.38); 3.2175 (0.32); 3.0961 (0.41); 3.0623 (0.35); 2.9842 (0.35); 2.8907 (1.32); 2.83 (0.8); 2.8117 (0.8); 2.7313 (0.96); 2.6766 (1.05); 2.6721 (1.47); 2.6675 (1.09); 2.5424 (0.67); 2.5255 (2.36); 2.5208 (3.63); 2.512 (75.12); 2.5075 (162.37); 2.503 (218.4); 2.4984 (156.12); 2.494 (73.27); 2.3388 (0.55); 2.3342 (1.08); 2.3297 (1.5); 2.3252 (1.13); 1.99 (16); 1.7116 (3.31); 1.6105 (0.4); 1.5971 (0.55); 1.5894 (0.58); 1.576 (0.43); 1.4981 (0.96); 1.458 (1.92); 1.44 (3.22); 1.4221 (1.86); 1.4094 (0.97); 1.3406 (3.68); 1.3235 (3.33); 1.3135 (3.04); 1.2956 (3.01); 1.2777 (2.74); 1.2582 (2.19); 1.2343 (5.2); 1.2036 (1.29); 1.1922 (5.62); 1.1863 (2.32); 11744 (10.68); 1.1676 (3.46); 1.1566 (7.96); 1.1448 (5.05); 1.1332 (3.63); 1.1153 (1.98); 1.0491 (1.91); 0.9496 (1.15); 0.9317 (1.85); 0.914 (0.87); 0.8933 (0.63); 0.8748 (1.42); 0.8624 (1.03); 0.8539 (1.15); 0.8363 (0.42); 0.1459 (0.45); 0.008 (3.24); -0.0002 (113.96); -0.0085 (3.81); -0.1496 (0.43

Application 53, solvent: IDMSOI, spectrometer: 399.95 MHz 11.4811 (0.46); 9.5802 (3.86); 9.504 (0.61); 7.8067 (0.33); 7.7817 (3.36); 7.7747 (1.02); 7.7681 (1.19); 7.7604 (4.49); 7.7135 (0.41); 7.6917 (0.47); 7.6851 (0.47); 7.5943 (0.9); 7.5726 (1.01); 7.3651 (0.37); 4.106 (0.36); 4.0549 (0.76); 4.037 (2.46); 4.0205 (16); 4.0015 (0.98); 3.4808 (0.47); 3.4264 (0.76); 3.4141 (1.01); 3.366 (481.46); 3.3609 (380.93); 3.3594 (381.76); 3.3541 (595.63); 3.3505 (698.07); 3.0316 (0.61); 2.6772 (1.33); 2.6727 (1.85); 2.6681 (1.36); 2.5429 (0.97); 2.5261 (3.27); 2.5213 (4.97); 2.5126 (89.86); 2.5081 (194.5); 2.5036 (263.53); 2.4991 (189.65); 2.4946 (89.56); 2.4051 (1.69); 2.335 (1.23); 2.335303 (1.72); 2.3258 (1.27); 2.0763 (1.33); 2.0394 (9.05); 1.9899 (10.76); 1.9092 (0.76); 1.6335 (1.56); 1.6194 (3.67); 1.6124 (4.01); 1.5991 (1.94)3; 1.5757 (0.35); 1.3543 (0.43); 1.2973 (1.85); 1.2837 (3.68); 1.277 (4.01); 1.2623 (1.85); 1.2521 (0.95); 1.2369 (1.14); 1.1922 (2.96); 1.1744 (5.8); 1.1566 (2.83); 0.008 (0.76); -0.0002 (21.52); -0.0085 (0.61

Application 54, solvent: IDMSOI, spectrometer: 399.95 MHz 9.4882 (0.79); 9.3813 (4.43); 8.5176 (2.05); 8.5137 (2.27); 8.5056 (2.27); 8.5017 (2.28); 8.4323 (3.23); 8.4273 (3.41); 8.2561 (0.5); 8.2509 (0.53); 7.952 (0.59); 7.7143 (0.68); 7.7082 (0.72); 7.6847 (1.07); 7.686801 (1.7); 7.6753 (1.15); 7.6651 (1.28); 7.6603 (1.95); 7.6556 (1.27); 7.5766 (0.52); 7.555 (0.77); 7.5036 (2.71); 7.4973 (2.86); 7.4812 (0.43); 7.4689 (0.59); 7.4626 (0.76); 7.4508 (4.33); 7.4415 (0.51); 7.4293 (4.72); 7.4088 (1.88); 7.3969 (1.79); 7.3893 (1.66); 7.3773 (1.57); 6.9932 (1.56); 6.9868 (1.58); 6.9719 (1.46); 6.9654 (1.45); 5.4683 (2.14); 5.4307 (2.45); 5.0433 (0.53); 4.9943 (0.63); 4.9816 (2.41); 4.9544 (0.36); 4.9441 (2.09); 4.0808 (2.62); 4.0555 (0.62); 4.0377 (1.82); 4.02 (1.85); 4.0022 (0.63); 3.9068 (16); 3.3269 (326.92); 3.322 (337.09); 2.8902 (5.17); 2.7304 (4.11); 2.6791 (0.48); 2.675 (1.04); 2.6704 (1.48); 2.6658 (1.11); 2.6613 (0.56); 2.5408 (0.86); 2.5237 (2.77); 2.5102 (73.18); 2.5058 (152.67); 2.5013 (207.94); 2.4967 (155.09); 2.4923 (79.01); 2.337 (0.46); 2.3326 (1.01); 2.3281 (1.42); 2.3235 (1.05); 2.3191 (0.53); 2.0737 (0.39); 1.9884 (7.83); 1.6127 (2.1); 1.5986 (4.95); 1.5917 (5.39); 1.5785 (2.38); 1.2787 (0.41); 1.2653 (0.83); 1.2583 (1.18); 1.2433 (0.76); 1.2353 (1.12); 1.2176 (1.97); 1.204 (4.14); 1.1973 (4.51); 1.1924 (3.36); 1.183 (1.78); 1.1745 (4.42); 1.1567 (2.17); 0.008 1.38); -0.0002 (45.87); -0.0084 (2.11

Application 55, solvent: IDMSOI, spectrometer: 399.95 MHz 9.4969 (1.3); 9.3847 (4.47); 7.9522 (0.67); 7.6698 (0.96); 7.664 (1.17); 7.6364 (0.52); 7.615 (1.61); 7.6008 (1.05); 7.5951 (0.94); 7.5792 (0.35); 7.5731 (0.36); 7.507 (3.9); 7.4855 (4.65); 7.4513 (3.32); 7.4447 (3.77); 7.2367 (2.05); 7.2301 (2.11); 7.2153 (1.83); 7.2086 (1.89); 4.9577 (1.05); 4.9518 (1.43); 4.9482 (1.23); 4.8765 (3.22); 4.7971 (5.72); 4.7583 (2.3); 4.7061 (0.96); 4.3904 (2.06); 4.3516 (1.9); 4.3323 (0.37); 4.2925 (0.75); 4.2475 (0.75); 4.2081 (0.32); 4.0563 (5.38); 4.0379 (2.52); 4.0201 (2.62); 4.0023 (0.85); 3.9551 (0.69); 3.8648 (16); 3.6011 (0.36); 3.5766 (15.78); 3.3572 (0.33); 3.3255 (554.45); 2.8905 (5.77); 2.731 (4.53); 2.6751 (0.77); 2.6707 (1.1); 2.666 (0.83); 2.5407 (0.36); 2.524 (1.72); 2.5105 (54.47); 2.5061 (115.62); 2.5015 (158.95); 2.497 (121.97); 2.4927 (65.07); 2.39327 (0.86); 2.3283 (1.14); 2.3238 (0.89); 2.1326 (0.37); 2.1203 (5.45); 1.9886 (10.49); 1.7799 (6.3); 1.7121 (13.9); 1.6499 (0.4); 1.6077 (2.28); 1.5936 (5.52); 1.5872 (5.41); 1.5736 (3.14); 1.5679 (4.32); 1.2928 (0.62); 1.2791 (1.24)3; 1.2727 (1.44); 1.2583 (0.93); 1.2352 (1.63); 1.2184 (1.97); 1.205 (4.02); 1.1984 (4.28); 1.1924 (4); 1.1846 (1.85); 1.1745 (5.9); 1.1568 (3.09); 1.1023 (0.52); 1.0152 (11.7); 0.9974 0.34); -0.0002 (0.61

Application 56, solvent: IDMSOI, spectrometer: 601.6 MHz 9.4759 (0.64); 9.3699 (3.96); 8.5556 (5.83); 8.5529 (3.5); 8.5482 (3.58); 8.5456 (6.22); 8.4651 (0.81); 8.4626 (0.53); 8.4577 (0.53); 8.4551 (0.83); 7.9522 (0.41); 7.7446 (0.57); 7.5812 (1.4); 7.5194 (2.55); 7.5151 (2.6); 7.4619 (4.25); 7.4476 (4.7); 7.2711 (4.79); 7.2612 (4.76); 7.1362 (0.73); 7.1264 (0.73); 7.1037 (1.56); 7.0993 (1.54); 7.0894 (1.48); 7.0849 (1.45); 5.4328 (2.05); 5.4068 (2.29); 5.0763 (0.44); 5.0253 (2.42); 4.9994 (2.01); 4.0725 (2.43); 4.0467 (1.03); 4.0348 (2.93); 4.023 (2.97); 4.0112 (0.99); 3.9285 (16); 3.3673 (0.36); 3.3234 (775.68); 3.2995 (6.23); 2.8904 (3.65); 2.739311 (2.88); 2.6191 (0.72); 2.6161 (1.53); 2.6131 (2.16); 2.61 (1.53); 2.607 (0.72); 2.5406 (0.65); 2.5377 (0.44); 2.5223 (5.37); 2.5193 (6.39); 2.5162 (5.82); 2.5074 (108.34); 2.5044 (234.17); 2.5013 (320.07); 2.4983 (230.08); 2.4953 (105.4); 2.3916 (0.64); 2.3885 (1.45); 2.3855 (2.03); 2.3824 (1.42); 2.3794 (0.63); 2.0737 (0.79); 1.9885 (12.97); 1.604 (2.16); 1.5948 (4.81); 1.5903 (5.36); 1.5814 (2.18); 1.2674 (0.33); 1.2583 (0.74); 1.2538 (0.79); 1.2441 (0.52); 1.2351 (0.55); 1.2076 (1.71); 1.1984 (3.86); 1.1941 (4.14); 1.1863 (4.31); 1.1745 (7.06); 1.1626 (3.5); 0.0965 (0.4); 0.0052 (3.02); -0.0002 (99.19); -0.0058 (2.91); -0.1001 (0.39

Application 57, solvent: IDMSOI, spectrometer: 399.95 MHz 11.5339 (4.33); 9.4933 (1.31); 9.4791 (5.1); 7.778683 (0.46); 7.7659 (1.88); 7.7568 (1.13); 7.7496 (4.1); 7.7332 (1.88); 7.697 (8.58); 7.6917 (3.71); 7.6793 (3.75); 7.6736 (2.13); 7.6497 (0.47); 7.6332 (0.74); 7.6173 (0.48); 7.586851 (3.7); 7.567 (1.83); 7.5617 (2.51); 7.5506 (0.43); 7.5346 (0.34); 7.5192 (0.33); 5.9815 (0.48); 5.9665 (0.79); 5.95 (0.57); 5.9152 (0.52); 5.8999 (0.51); 5.8617 (1.01); 5.8285 (6.59); 5.8124 (6.52); 5.3477 (1.24); 5.3423 (1.27); 4.0562 (1.36); 4.0382 (3.76); 4.0202 (3.91); 4.0025 (1.35); 3.9786 (1.07); 3.6883 (0.81); 3.5728 (0.36); 3.5567 (0.37); 3.5234 (0.37); 3.5028 (0.42); 3.4858 (0.46); 3.4778 (0.41); 3.4639 (0.45); 3.4477 (0.59); 3.4164 (0.76); 3.3245 (1168.23); 3.2622 (0.43); 3.2123 (0.32); 3.1803 (0.58); 3.1683 (0.47); 3.0473 (1.21); 2.9933 (4.69); 2.9063 (0.59); 2.8597 (1.25); 2.8422 (4.92); 2.6749 (3.65); 2.6707 (4.76); 2.6666 (3.51); 2.5505 (1.32); 2.5403 (2.36); 2.5237 (16.88); 2.506 (550.85); 2.5017 (693.41); 2.4974 (500.71); 2.438 (0.61); 2.4143 (0.41); 2.393 (0.38); 2.3369 (10); 2.3286 (4.78); 2.3239 (3.48); 2.2986 (0.44); 2.2881 (0.35); 2.2187 (0.35); 2.1917 (0.47); 2.074 (0.97); 2.0503 (0.97); 1.9889 (16); 1.6079 (2.47); 1.5934 (6.31); 1.5869 (6.86); 1.5737 (3.53); 1.5483 (0.66); 1.5334 (0.56); 1.3133 (0.48); 1.2989 (0.51); 1.2759 (2.83); 1.2618 (6.03); 1.2551 (6.78); 1.2402 (4.56); 1.1923 (4.5); 1.1745 (8.44); 1.1571 (4.12); 0.8537 (0.55); 0.0077 (1.92); 0.0004 (50.97); -0.0002 (51.39); -0.0076 (2.47

Application 58, solvent: IDMSOI, spectrometer: 399.95 MHz 11.4625 (0.76); 9.4924 (0.91); 7.7342 (0.69); 7.7279 (0.87); 7.6972 (0.38); 7.6754 (0.52); 7.669 (0.44); 7.5846 (0.89); 7.5628 (0.61); 5.2886 (0.42); 5.2653 (0.38); 5.2629 (0.4); 5.2177 (0.4); 5.2149 (0.4); 5.1751 (0.34); 5.1722 (0.34); 5.0002 (0.7); 4.9854 (0.68); 4.0553 (1.25); 4.0375 (3.8); 4.0197 (3.84); 4.0019 (1.29); 3.3327 (56.56); 2.5244 (0.53); 2.5107 (9.02); 2.5065 (18.16); 2.502 (23.94); 2.4976 (17.52); 2.4933 (8.69); 1.9892 (16); 1.6078 (0.32); 1.5935 (0.8); 1.5866 (0.87); 1.5734 (0.97); 1.2731 (0.38); 1.2595 (0.79); 1.2527 (0.87); 1.2381 (0.4); 1.1924 (4.32); 1.1746 (8.51); 1.1568 (4.22

Application 59, solvent: IDMSOI, spectrometer: 399.95 MHz 11.651 (3.43); 9.5701 (3.87); 7.8258 (0.42); 7.8066 (0.45); 7.786856 (1.77); 7.7798 (1.75); 7.7597 (1.67); 7.7539 (1.75); 7.4937 (2.27); 7.4912 (2.53); 7.4879 (2.46); 4.055 (1.17); 4.0364 (16); 4.0195 (2.96); 4.0017 (0.96); 3.3272 (189.39); 3.3038 (1.7); 2.6753 (2.02); 2.6707 (2.77); 2.6662 (2.03); 2.6617 (1); 2.5409 (1.96); 2.538 (2); 2.5241 (10.07); 2.5194 (14.6); 2.5106 (143.21); 2.5062 (290.59); 2.5017 (381.24); 2.4971 (273.16); 2.4927 (130.54); 2.3372 (0.88); 2.3329 (1.89); 2.3284 (2.64); 2.3238 (1.92); 1.9891 (12.1); 1.6247 (1.42); 1.6106 (3.42); 1.6037 (3.59); 1.5904 (1.59); 1.339354 (0.45); 1.2977 (0.37); 1.2887 (1.71); 1.2751 (3.39); 1.2684 (3.63); 1.254 (1.5); 1.2493 (0.86); 1.2349 (1.15); 1.1921 (3.43); 1.1743 (6.77); 1.1565 (3.32); 0.146 (0.95); 0.008 (8.15); -0.0002 (242.95); -0.0085 (7.93); - 0.1497 (0.89

Application 60, solvent: IDMSOI, spectrometer: 399.95 MHz 7.194 (4.24); 7.7727 (4.24); 7.6351 (0.76); 4.0377 (0.78); 4.0274 (0.64); 4.0196 (1.38); 4.0064 (16); 3.3192 (128.67); 3.2968 (0.7); 2.8209 (1.39); 2.8055 (1.44); 2.6747 (0.95); 2.6701 (1.33); 2.6657 (0.98); 2.5404 (0.79); 2.5235 (3.49); 2.51 (67.6); 2.5057 (137.84); 2.5011 (183.23); 2.4966 (131.99); 2.4922 (63.54); 2.4323 (0.41); 2.414 (0.36); 2.3324 (1.13); 2.3278 (1.54); 2.3234 (1.25); 2.3189 (0.84); 2.2912 (1.59); 2.2752 (1.59); 1.9886 (2.92); 1.8835 (2.17); 1.6149 (0.87); 1.4668 (0.4); 1.449 (0.35); 1.3351 (0.44); 1.2492 (0.66); 1.2339 (0.36); 1.1922 (0.88); 1.1744 (1.71); 1.1566 (0.85); 1.1112 (0.34); 1.0892 (0.48); 1.084 (0.4); 1.0655 (0.87); 1.0372 (4.91); 1.0194 (10.33); 1.0015 (4.75); 0.9043 (4.3); 0.8866 (9.1); 0.8688 (4.15); 0.008 (1.09); -0.0002 (32.33); -0.0085 (1.18

Application 61, solvent: IDMSOI, spectrometer: 399.95 MHz 11.5111 (0.37); 11.475 (1.82); 7.8171 (0.36); 7.761 (1.76); 7.7563 (1.78); 7.6607 (0.63); 7.6561 (0.62); 7.6393 (1.64); 7.6344 (1.68); 7.6196 (2.16); 7.5979 (0.65); 4.0388 (7.82); 4.0199 (1.67); 3.3272 (155.76); 3.3046 (0.44); 3.2089 (0.61); 3.0604 (0.48); 2.8649 (0.47); 2.6801 (0.39); 2.6754 (0.85); 2.6708 (1.18); 2.6662 (0.84); 2.6616 (0.37); 2.541 (0.64); 2.5242 (3.65); 2.5194 (6.12); 2.5108 (63.64); 2.5063 (126.44); 2.5017 (165.51); 2.4971 (117.67); 2.4926 (54.8); 2.3375 (0.45); 2.333 (0.89); 2.3285 (1.2); 2.3239 (0.84); 2.3193 (0.4); 1.9892 (1.79); 1.717 (1.85); 1.4686 (0.61); 1.3975 (16); 1.335356 (0.56); 1.3185 (0.45); 1.3025 (0.73); 1.2491 (0.7); 1.2357 (0.51); 1.2144 (1.84); 1.1967 (3.53); 1.179 1.74); 1.1744 (1.8); 1.1565 (0.59); 0.008 (0.73); -0.0002 (19.27); -0.0085 (0.58

Application 62, solvent: IDMSOI, spectrometer: 399.95 MHz 11.4809 (1.28); 7.786806 (1.15); 7.7762 (1.17); 7.6487 (0.33); 7.6426 (0.35); 7.6268 (1.18); 7.6215 (1.31); 7.6147 (1.72); 7.593 (0.33); 4.0556 (0.42); 4.0348 (5.9); 4.0202 (1.98); 4.0022 (0.4); 3.3283 (21.01); 3.1067 (0.99); 2.8649 (5.51); 2.5245 (0.58); 2.511 (9.79); 2.5067 (19.73); 2.5022 (26.27); 2.4977 (19.46); 2.4934 (9.59); 1.9895 (4.55); 1.6728 (1.36); 1.4933 (1.02); 1.3975 (16); 1.1926 (1.27); 1.1748 (2.51); 1.157 (1.23); -0.0002 (2.53

Application 63, solvent: IDMSOI, spectrometer: 399.95 MHz 9.6002 (1.23); 7.7269 (1.04); 7.7055 (1.24); 7.6766 (0.93); 7.6704 (0.97); 7.4809 (0.56); 7.4747 (0.53); 7.4597 (0.48); 7.4533 (0.47); 4.8951 (0.42); 4.8795 (0.59); 4.864 (0.43); 4.0855 (4.08); 4.0568 (1.41); 4.039 (4.12); 4.0212 (4.16); 4.0034 (1.43); 3.3262 (2.69); 2.5117 (1.75); 2.5073 (3.52); 2.5028 (4.67); 2.4983 (3.47); 2.4939 (1.71); 1.9898 (16); 1.617 (0.42); 1.6028 (1.05); 1.596 (1.11); 1.5828 (0.47); 1.2947 (0.5); 1.281 (1.05); 1.2745 (1.1); 1.2599 (0.4); 1.1934 (5.01); 1.1756 (9.46); 141578 4.87); 1.0379 (1.17); 1.0225 (1.27); 0.994 (1.27); 0.9787 (1.15); -0.0002 (1.31

Application 64, solvent: IDMSOI, spectrometer: 399.95 MHz 11.531 (5.19); 9.4981 (6.09); 8.3176 (0.59); 7.7614 (4.9); 7.7551 (5.67); 7.69 (2.44); 7.686836 (2.05); 7.6681 (3.54); 7.6617 (3.29); 7.588 (6.35); 7.5661 (4.3); 5.5721 (1.17); 5.5509 (3.42); 5.5291 (3.53); 5.5072 (1.24); 4.0553 (0.61); 4.0375 (1.86); 4.0197 (1.88); 4.0019 (0.63); 3.3757 (6.9); 2.6756 (1.2); 2.671 (1.66); 2.6665 (1.24); 2.5379 (1.15); 2.5242 (6.33); 2.5193 (9.89); 2.5108 (89.72); 2.5065 (179.68); 2.5019 (237.24); 2.4974 (175.66); 2.4931 (88.49); 2.3331 (1.22); 2.3287 (1.67); 2.3242 (1.26); 1.989 (7.98); 1.609 (2.14); 1.5947 (5.27); 1.5878 (5.67); 1.5746 (2.44); 1.3977 (16); 1.3122 (0.32); 1.2725 (2.58); 1.2588 (5.23); 1.2521 (5.65); 1.2375 (2.18); 1.1926 (2.19); 1.1748 (4.28); 1.157 2.11); 0.8854 (0.38); 0.0079 (1.5); -0.0002 (40.02); -0.0083 (1.91

The intensity of the sharp signals correlates with the height of the signals in the printed example of the NMR spectrum in cm and shows the true ratio of the signal intensities. In the case of broad signals, several peaks or the middle of the signal and their relative intensities can be plotted against the most intense signal in the spectrum.

H NMR peak lists are similar to conventional H NMR printouts and thus usually contain all peaks listed in conventional NMR representations.

In addition, like conventional H NMR prints, they may show solvent signals, signals of stereoisomers of target compounds that similarly form part of the subject matter of the invention, and/or impurity peaks.

In the combined signals of compounds in the delta range of solvents and/or water, our lists of "H

NMR peaks show common solvent peaks, such as the DMSO peaks in DMSO-sbv and the water peak, which usually have high intensity on average.

Stereoisomeric peaks of the target compounds and/or impurity peaks usually have on average less intensity than the peaks of the target compounds (for example, with a purity of 290 9b).

Such stereoisomers and/or impurities may be characteristic of a particular production method. Their peaks can thus help to identify the reproduction of our method based on such "byproduct fingerprints".

A specialist in the field of calculation of peaks of target compounds by known methods (MeziteS, ASO modeling, as well as the use of empirically estimated expected values) can, if necessary, highlight the peaks of target compounds, optionally with the use of additional intensity filters. This selection will be analogous to the selection of relevant peaks in the traditional interpretation of "H NMR.

Obtaining starting substances

Ethyl 3-(1-chlorocyclopropyl)-1-methyl-1H-pyrazole-5-carboxylate

IF)

In ros" "7 sn. 9 10.16 g (254.2 mmol) of sodium hydride is suspended in 125 ml of tetrahydrofuran, d.o.a. and cooled to -15 "С. A solution of 15.0 g (127.1 mmol) of 1-(1-chlorocyclopropyl)ethanone in 25 ml of tetrahydrofuran n.o.s. is added dropwise to this suspension. The suspension is stirred at -1570 for 2 hours, and then 37.12 g (254.2 mmol) of diethyl oxalate is added. After three hours at room temperature, the reaction is quenched with ice water. The aqueous phase is repeatedly extracted with ethyl acetate. The combined organic phases are washed with saturated sodium chloride solution, dried over sodium sulfate and filtered. The solvent is removed on a rotary evaporator under reduced pressure.

The residue is dissolved in 150 ml of ethanol. and boil under reflux. 36.09 g (254.2 mmol) of methylhydrazine sulfate is added to the mixture under reflux, and the mixture is refluxed for an additional 4 hours. After cooling, the reaction mixture is concentrated under reduced pressure on a rotary evaporator, and the residue thus obtained is added to a mixture of water and ethyl acetate. The aqueous phase is repeatedly extracted with ethyl acetate. The combined organic phases are washed with saturated sodium chloride solution, dried over sodium sulfate and filtered. The solvent is removed on a rotary evaporator under reduced pressure. The crude product was purified by column chromatography to give 4.34 g (15595) of ethyl 3-(1-chlorocyclopropyl)-1-methyl-1H-pyrazole-5-carboxylate. "H-NMR (300 MHz, ag-chloroform) 5 - 6.89 (5, 1H), 4.36 (d, 2H), 4.11 (5, ЗН), 1.35 (и, ЗН) ppm;

Ethyl 4-chloro-3-(1-chlorocyclopropyl)-1-methyl-1H-pyrazole-5-carboxylate

SI

IF)

M X o-./ Oz 7" sn. 9,500 mg (2.19 mmol) of ethyl 3-(1-chlorocyclopropyl)-1-methyl-1H-pyrazole-5-carboxylate is dissolved in 10 ml of M, M-dimethylformamide ch.d .a., and add 438 mg (3.28 mmol) of M-chlorosuccinimide. The reaction mixture is heated at 80 "C for 15. The cooled reaction solution is diluted with water and extracted twice with ethyl acetate. Combined organic phases

It is washed with a saturated solution of sodium chloride, dried over sodium sulfate and filtered.

The solvent is removed under reduced pressure on a rotary evaporator. The crude product is filtered through silica gel and eluted with ethyl acetate. This gives 517 mg (8095) of ethyl 4-chloro-3-(1-chlorocyclopropyl)-1-methyl-1H-pyrazole-5-carboxylate with a purity of 89 95. "H-NMR (400 MHz, α6-DMSO): b - 4.35 (d, 2H), 4.04 (5, ЗН), 1.42-1.46 (t, 2H), 1.31-1.38 (t, 5H)

M.D.

HPLC-MS 2): IsdR-3.52, mass (p/z) - 263 |MA-NI"". 4-Chloro-3-(1-chlorocyclopropyl)-1-methyl-1H-pyrazole-5-carboxylic acid

SI

IF) i

517 mg (1.76 mmol) of ethyl 4-chloro-3-(1-chlorocyclopropyl)-1-methyl-1H-pyrazole-5-carboxylate (purity 89-95) was dissolved in 10 ml of ethanol . Then 3.5 ml (3.5 mmol) of 1 n. aqueous solution of sodium hydroxide, and the mixture is stirred at room temperature for 16 hours. The reaction mixture is acidified by adding 1 n. hydrochloric acid. The aqueous phase is extracted twice with ethyl acetate. The combined organic phases are washed with saturated sodium chloride solution, dried over sodium sulfate and filtered. The solvent is removed under reduced pressure on a rotary evaporator. This gives 422 mg (99965) of 4-chloro-3-(1-chlorocyclopropyl)-1-methyl-1H-pyrazole-5-carboxylic acid. "H-NMR (400 MHz, ae-DMSO): 6 - 4.02 (5, ЗН), 1.31-1.42 (t, 4Н) ppm.

HEV-MS 2): IsdR-1.90, mass (t/2) - 235 (MANI.

Ethyl 3-(1-fluorocyclopropyl)-1-methyl-1H-pyrazole-5-carboxylate

IS

7 sleep 9

Ethyl 3-(1-fluorocyclopropyl)-1-methyl-1H-pyrazole-o-carboxylate is obtained from /1-(1-fluorocyclopropyl)ethanone similarly to the method described in the synthesis of ethyl 3-(1-chlorocyclopropyl)-1-methyl- 1H-pyrazole-5-carboxylate. "H-NMR (300 MHz, ag-chloroform) b - 6.90 (5, 1H), 4.34 (d, 2H), 4.13 (5, ЗН), 1.37 (Й, ЗН) ppm;

Ethyl 4-chloro-3-(1-fluorocyclopropyl)-1-methyl-1H-pyrazole-5-carboxylate

SI

IS

M. H. o. UN 7" sleep 9

The preparation was carried out similarly to the preparation of ethyl 4-chloro-3-(1-chlorocyclopropyl)-1-methyl-1H-pyrazole-5-carboxylate, using ethyl 3-(1-fluorocyclopropyl)-1-methyl-1H-pyrazole-5- carboxylate and with eq. M-chlorosuccinimide. "H-NMR (400 MHz, ae-DMSO): b - 4.36 (d, 2H), 4.06 (5. ЗН), 1.38-1.44 (t, 2Н), 1.33 (I, ЗН), 1.04-1.09 (t , 2H) m.d.

HPLC-MS 2): IsdR-3.07, mass (t/2) 5,247 (MANI. 4-Chloro-3-(1-fluorocyclopropyl)-1-methyl-1H-pyrazole-5-carboxylic acid

SI

IS

M. I

And sleep 9

The preparation was carried out similarly to the preparation of 4-chloro-3-(1-chlorocyclopropyl)-1-methyl-1 H-

From pyrazole-5-carboxylic acid, using ethyl 3-(1-fluorocyclopropyl)-1-methyl-1H-pyrazole-

B-carboxylate and 5.0 equiv. of sodium hydroxide in methanol. "H-NMR (400 MHz, ae-DMSO): b - 4.05 (5, ЗН), 1.37-1.43 (t, 2Н), 1.05-1.09 (t, 2Н) ppm.

HEV-MS 2): IsdR-3.07, mass (t/2) 5,219 (MANI.

Methyl 2-chloro-5-(C1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazol-5-yl)carbonylamino)benzoate

ES, SE" at bedtime

N (c) va

Step 9 4.0 g (12.8 mmol) of 1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxylic acid is suspended in 50 ml of dichloromethane. Then 0.02 ml of M, M-dimethylformamide and 3.54 ml (38.4 mmol) of oxalyl chloride are successively added. The reaction mixture is then stirred first at room temperature for 30 minutes and then under reflux for 30 minutes. The solvent is removed under reduced pressure on a rotary evaporator. The resulting 1-methyl-3-(pentafluoroethyl)-4-trifluoromethyl)-1H-pyrazole-5-carbonyl chloride is used for the next stage of synthesis without additional purification.

A solution of 4.24 g (12.8 mmol) of 1-methyl-3-(pentafluoroethyl)-4-trifluoromethyl)-1H-pyrazole-5-carbonyl chloride in 25 ml of dichloromethane n.o.s. is added to a suspension of 2.38 g (12.8 mmol ) of methyl 5-amino-2-chlorobenzoate and 2.57 g (19.2 mmol) of silver(I) cyanide in 50 ml of dichloromethane n.o.s., and the mixture was stirred at room temperature for 16 h. The suspension was then filtered through silica gel, and the product elute using a mixture of cyclohexane and ethyl acetate (1:1).

The organic phase is washed successively three times with 6 n. hydrochloric acid and twice saturated sodium chloride solution. The organic phase is then dried over sodium sulfate, filtered and concentrated on a rotary evaporator under reduced pressure. This gives 5.75 g (93,905) of methyl 2-chloro-5B-CI1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-ylcarbonyl)amino)benzoate. "H-NMR (400 MHz, dz-acetonitrile): b - 9.33 (5, 1H), 8.14 (y, 1), 7.72 (ai, 1H), 7.54 (y, 1H), 3.98 (5, ЗН), 3.90 (5, ZN) m.d.

HPLC-MS 2): IsdR-4.05, mass (t/2) - 480 (MANI. 2-Chloro-5-(11-methyl-3-(pentafluoroethyl)-4-"trifluoromethyl)-1H-pyrazole-5 - yl|carbonylamino)benzenecarboxylic acid

E.S, SE, Fr

N on

SI and about 5.75 g (11.9 mmol) of methyl 2-chloro-5-(11-methyl-3-(pentafluoroethyl)-4-"-trifluoromethyl)-1H-pyrazole-5-ylcarbonylamino)benzoate are dissolved in 30 ml of methanol. d.a., and then 15.0 mL (30.0 mmol) of 2N aqueous sodium hydroxide solution was added. The reaction mixture was stirred at room temperature for 16 hours. The reaction solution was carefully acidified with 1N hydrochloric acid, and the aqueous phase was then extracted three times with ethyl acetate The combined organic phases are washed once with saturated sodium chloride solution, dried over sodium sulfate

Zo and filter. The solvent is removed under reduced pressure on a rotary evaporator. This gives 5.57 g of 2-chloro-5-C11-methyl-3-(pentafluoroethyl)-4-trifluoromethyl)-1H-pyrazol-5-yl(carbonyl)amino)benzenecarboxylic acid as a colorless solid. "H-NMR (400 MHz, dz-acetonitrile): b - 9.17 (5, 1H), 8.11 (y, 1), 7.73 (aa, 1H), 7.52 (9, 1), 3.98 (5, ЗН) m .d.

VERH-MS 2): IsdR-3.18, mass (t/2) - 466 (MANI.

Ethyl 3,4-bis(trifluoromethyl)-1H-pyrazole-5-carboxylate

SE. SE.

And they

M.

M

NOT about

In an atmosphere of protective gas, 7.57 g (63.0 mmol) of diazoethyl acetate is first placed in 200 ml of diethyl ether, and the temperature of the mixture is set to -70 "C. Then, 20.4 g (126 mmol) of hexafluorobutyne is introduced into the cooled solution. The reaction mixture is slowly heated to room temperature and stirred for 16 hours. The solvent was then removed on a rotary evaporator. This gave 17.0 g of ethyl 3,4-bis(trifluoromethyl)-1H-pyrazole-5-carboxylate (98 Fo) as a yellow oil. "H-NMR (400 MHz , az-acetonitrile): b - 4.42 (d, 2H), 1.38 (i, ЗН) ppm.

GC-MS: retention time 3.48 min.; mass (t/2) - 276 |MI". 1-Methyl-3,4-bistrifluoromethyl)-1H-pyrazole-5-carboxylic acid

EC CE

/

MK con her (6) sn, 3.0 g (10.9 mmol) of ethyl 3,4-bis(trifluoromethyl)-1H-pyrazole-5-carboxylate and 4.5 g (32.6 mmol) of potassium carbonate are suspended in 70 ml of acetone, and 1.35 ml of iodomethane (21.7 mmol).

The reaction mixture was stirred at room temperature overnight. 54 ml (108 mmol) of 2 n. aqueous solution of sodium hydroxide. The solution is then stirred at room temperature overnight. The reaction mixture is diluted with water, and most of the acetone is removed on a rotary evaporator under reduced pressure. The pH value of the residue was set to 2-3 using 1 M hydrochloric acid. The aqueous reaction solution was extracted twice with ethyl acetate. The combined organic phases are dried over magnesium sulfate, filtered and concentrated under reduced pressure on a rotary evaporator. This gives 2.7 g of 1-methyl-3,4-bis(trifluoromethyl)-1H-pyrazole-5-carboxylic acid (84 95; purity 88 95) as a brown solid. "H-NMR (400 MHz, dz-acetonitrile): b - 4.12 (5, ЗН) ppm

VERH-MS 2): IsdR-1.47, mass (t/2) - 263 (MANI.

Methyl 2-chloro-5-(methylamino)benzoate no

MN

FI thing

Sn

SI i) 55.0 g (296 mmol) of methyl 2-chloro-5-aminobenzoate and 49.1 g (356 mmol) of potassium carbonate are suspended in 500 ml of acetonitrile n.d.a. 22.1 ml (356 mmol) of methyl iodide was added dropwise to the reaction mixture. The suspension is then refluxed for 3 hours.

After cooling, the reaction mixture is filtered. The filtrate is diluted with water. The aqueous phase is extracted twice with ethyl acetate. The combined organic phases are dried over sodium sulfate and filtered. The solvent is removed under reduced pressure on a rotary evaporator. The crude product is purified by column chromatography. This gives 30.0 g (51 95) of methyl 2-chloro-5-(methylamino)benzoate. "H-NMR (300 MHz, ai-chloroform) b - 7.21 (a, 1H), 7.00 (a, 1H), 6.63 (y, 1H), 3.90 (5, ЗН), 2.86 (5, ЗН) m. d.

Zo B-Amino-2-chloro-M-(1-cyanocyclopropyl)benzamide

MH,

M in her

M

SI i) 3.20 g (15.9 mmol) of 2-chloro-5-nitrobenzoic acid is first placed in 50 ml of dichloromethane n.o., and 0.06 ml of M, M-dimethylformamide n.o. is added. Then 2.08 ml (23.8 mmol) of oxalyl chloride was added to the reaction mixture. After three hours at RT, the reaction mixture is concentrated under reduced pressure on a rotary evaporator. The crude product (2-chloro-5-nitrobenzoyl chloride) is introduced into the further reaction without additional purification. 2.36 g (19.8 mmol) of 1-aminocyclopropanecarbonitrile hydrochloride is suspended in 70 ml of chloroform n.d.a. When cooled with ice, 6.93 ml (39.7 mmol) of M-ethyldiisopropylamine is added to the suspension. Then a solution of 3.50 g (15.9 mmol) of 2-chloro-5-nitrobenzoyl chloride in 5 ml of chloroform n.o.a. is added dropwise to the cooled mixture. The reaction mixture is heated at 50"C (oil bath temperature) for 4 hours. The reaction mixture is then stirred at room temperature for another 12 hours.

The reaction mixture is concentrated under reduced pressure on a rotary evaporator, and the residue is taken up in ethyl acetate. The organic phase is washed twice with 0.5 N. hydrochloric acid, dried over sodium sulfate and filtered. The solvent is removed under reduced pressure on a rotary evaporator. This gives 3.70 g (84 95) of 2-chloro-N-(1-cyanocyclopropyl)-5-nitrobenzamide. "H-NMR (400 MHz, a6e-DMSO): b - 9.59 (5, 1H), 8.36 (a, 1H), 8.31 (aa, 1h), 7.85 (a, 1H), 1.55-1.61 (t, 2H ), 1.32-1.37 (t, 2H) ppm.

HPLC-MS 2): IsdR-1.52, mass (t/2) - 266 (MANI. 3.15 g of iron powder is suspended in 18 ml of 595% acetic acid, and a solution of 3.0 g of 2-chloro-M-(1 -cyanocyclopropyl)-5-nitrobenzamide in a mixture of 25 ml of ethyl acetate and 22.6 ml of glacial acetic acid. During the addition, the internal temperature is maintained below 45 "C. The reaction mixture is stirred at room temperature for 14 hours and then filtered through celite. The filtrate is diluted with water, and the aqueous phase was extracted three times with ethyl acetate. The combined organic phases were washed twice with saturated sodium chloride solution, dried over magnesium sulfate, filtered, and concentrated on a rotary evaporator under reduced pressure. The crude product was triturated with a mixture of three parts cyclohexane and one part ethyl acetate, and the solid was filtered off. This gave 2.0 g (71 95) of 5-amino-2-chloro-N-(1-cyanocyclopropyl)benzamide. "H-NMR (400 MHz, a6e-DMSO): b - 9.20 (5, 1H) , 7.07 (a, 1H), 6.62 (aa, 1H), 6.57 (a, 1H), 1.51-1.57 (t, 2H), 1.17-1. 24 (t, 2H) m.d.

HPLC-MS 2): IsdR-0.82, mass (t/2) - 236 (MANI. 1-Methyl-4-(methylsulfanyl)-3-(pentafluoroethyl)-1H-pyrazole-5-carboxylic acid

IS

ZK

E 5-

M M on

M o 8.0 g (27.7 mmol) of 1-methyl-4-nitro-3-(pentafluoroethyl)-1H-pyrazole-o-carboxylic acid (obtained similarly to U. Mei. Spet. 1987, 30, 91-96) is dissolved in 100 ml of dichloromethane. 50 μl of M, M-dimethylformamide and 10.5 g (83.0 mmol) of oxalyl chloride are successively added to the solution. After 0.5 hours at room temperature, the reaction mixture is heated under reflux for 0.5 h. The reaction mixture is cooled to room temperature. Solvents and excess oxalyl chloride are removed on a rotary evaporator at

From reduced pressure. The residue is dissolved in chloroform n.d.a. and slowly add 5.56 g (41.5 mmol) of silver(I) cyanide, 100 ml of chloroform n.d.a. to the suspension. and 56 ml of methanol n.d.a.

The mixture is heated under reflux for 8 hours, and then cooled to room temperature. The reaction mixture is filtered through a short silica gel column, and the column is washed with dichloromethane. Solvents are removed on a rotary evaporator under reduced pressure.

This gives 8.5 g of methyl 1-methyl-4-nitro-3-(pentafluoroethyl)-1H-pyrazole-5-carboxylate. The crude product is used for the next reaction without additional purification. "H-NMR (600 MHz, ae-DMSO): 6 - 4.16 (5, ZN), 3.93 (5, ZN) ppm

VERH-MS 2): IsdR-3.18, mass (p/z) - 304 MANI". 8.5 g (28.0 mmol) of methyl 1-methyl-4-nitro-3-(pentafluoroethyl)-1H-pyrazole-5-carboxylate and 850 mg of palladium on carbon (10 95 palladium) are suspended in 100 ml of methanol. The autoclave is inert with nitrogen, and the reaction mixture is then stirred under a hydrogen atmosphere of 5 bar. After 22 hours at CT, the mixture is filtered through celite and the solvent is removed under reduced pressure on a rotary evaporator. The crude product is taken up in dichloromethane and filtered through sodium sulfate.

Dichloromethane is then removed under reduced pressure on a rotary evaporator.

This gives 6.7 g (86 95) of methyl 4-amino-1-methyl-3-(pentafluoroethyl)-1H-pyrazole-5-carboxylate. "H-NMR (600 MHz, ae-DMSO): 6 - 5.32 (5, 2H), 4.07 (5, ZN), 3.86 (5, ZN) ppm.

VERH-MS 2): IsdR-2.52, mass (p/z) - 274 |MANI". 2.0 g (7.32 mmol) of methyl 4-amino-1-methyl-3-(pentafluoroethyl)-1H-pyrazole-5-carboxylate and 1.38 g (14.6 mmol) of dimethyl disulfide are dissolved in 14 ml of acetonitrile n.a. A solution of 1.26 g (11.0 mmol) of tert-butyl nitrite in 5 ml of acetonitrile, d.o.a., is slowly added dropwise to this mixture. After the addition is complete, the reaction mixture is stirred at room temperature for a second 1 h. The reaction mixture is then poured into 1 n. hydrochloric acid. The aqueous phase is extracted three times with ethyl acetate. The combined organic phases are washed twice with saturated sodium chloride solution, dried over magnesium sulfate and filtered. Solvents are removed on a rotary evaporator under reduced pressure.

This gives 2.0 g (72 90) of methyl 1-methyl-4-(methylsulfanyl)-3-«(pentafluoroethyl)-1H-pyrazole-5-carboxylate as an 8:2 mixture of the target product and the by-product, methyl 1-methyl- 3-(pentafluoroethyl)-1H-pyrazole-5-carboxylate. "H-NMR (400 MHz, de-DMSO): b - 4.12 (5, ZN), 3.94 (5, ZN), 2.34 (5, ZN) ppm.

HPLC-MS 2): IsdR-3.51, mass (t/2) - 305 (MANI. 3.0 g of methyl 1-methyl-4-(methylsulfanyl)-3-(pentafluoroethyl)-1H-pyrazole-5-carboxylate is dissolved in 16 ml of methanol n.a. 16.5 ml of 2 N aqueous sodium hydroxide solution is then added to the solution, and the mixture is stirred at room temperature for 16 h. The reaction mixture is diluted with ethyl acetate and then washed with 100 ml of 1 N hydrochloric acid. The acidic aqueous phase extracted twice with ethyl acetate. The combined organic phases were washed with saturated sodium chloride solution, dried over sodium sulfate and filtered. The solvents were removed on a rotary evaporator under reduced pressure.

This gives 2.5 g (90 95) of 1-methyl-4-(methylsulfanyl)-3-(pentafluoroethyl)-1H-pyrazole-5-carboxylic acid as an approximately 8:2 mixture of the target product and the by-product, 1-methyl-3 - (pentafluoroethyl)-1H-pyrazole-5-carboxylic acid. "H-NMR (400 MHz, de-DMSO): b - 4.12 (5, ZN), 3.94 (5, ZN), 2.34 (5, ZN) ppm.

VERH-MS 2): IsdR-3.51, weight (t/2) - 305 (MANI.

Biological examples

A. Activity of compounds

Tests on Rpaedop (RNAESO, spray treatment)

Solvents: 78.0 mass parts of acetone and 1.5 mass parts of dimethylformamide

Emulsifier: 0.5 mass parts of alkylaryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 mass part of the active compound is mixed with the prescribed amounts of solvents and emulsifier, and the concentrate is diluted with water containing the emulsifier to the desired concentration. The plates of the leaves of Peking cabbage (Vgazzisa reKipepz5i) are sprayed with the preparation of the active compound of the desired concentration and, after

From drying, they are settled with larvae of the horseradish leaf-eater (Rpaedop sospieagiae).

After 7 days, determine the effectiveness, expressed in 100 9o means that all beetle larvae have died; 0 95 means that none of the beetle larvae died.

In this test, for example, the following compounds of the production examples show an efficiency of 100 95 at an application rate of 500 g/ha: 1,2,3,4,5,6, 7,8, 9,10.

Tests on 5-rodoriega and hydiregaa (ZROOERC, spray treatment)

Solvents: 78.0 mass parts of acetone and 1.5 mass parts of dimethylformamide

Emulsifier: 0.5 mass parts of alkylaryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 mass part of the active compound is mixed with the prescribed amounts of solvents and emulsifier, and the concentrate is diluted with water containing the emulsifier to the desired concentration. Plates of corn leaves (7ea tauvh) are sprayed with the composition of the active compound of the desired concentration and, after drying, are inhabited by caterpillars of the scoop (Zrodoriega Igidiregaa).

After 7 days, determine the efficiency expressed in 95. 100 9o means that all caterpillars have died; 0 9o means that none of the caterpillars died.

In this test, for example, the following combination of production examples shows an efficiency of 83 95 at an application rate of 500 g/ha: 7.

In this test, for example, the following compounds of production examples show an efficiency of 100 95 at an application rate of 500 g/ha: 2, 4, 5, 6, 8, 9, 10.

Tests on Mulyz5 (MU2ORE, spray treatment)

Solvents: 78 mass parts of acetone 1.5 mass parts of dimethylformamide

Emulsifier: 0.5 mass parts of alkylaryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 mass part of the active compound is mixed with the prescribed amounts of solvents and emulsifier, and the concentrate is diluted with water containing the emulsifier to the desired concentration. Plates of Beijing cabbage leaves (Vgazzisa rekKipepvi5), infested with peach green aphid of all stages (Muiz regzhisaye), are sprayed with the preparation of the active compound of the desired concentration.

After b days, the efficiency is determined, expressed in 95. 100 9o means that all aphid individuals have died; 0 95 means that none of the aphids died.

In this test, for example, the following compounds of the production examples show an efficiency of 90 95 at an application rate of 500 g/ha: 5, 9.

In this test, for example, the following compounds of production examples show an efficiency of 100 95 at an application rate of 500 g/ha: 2, 4, 6, 8, 10.

Tests on Teigapuspa5, OR-resistant (TETKIK, spray treatment)

Solvents: 78.0 mass parts of acetone and 1.5 mass parts of dimethylformamide

Emulsifier: 0.5 mass parts of alkylaryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 mass part of the active compound is mixed with the prescribed amounts of solvents and emulsifier, and the concentrate is diluted with water containing the emulsifier to the desired concentration. Plates of bean leaves (RpazeoYi5 mutchsiIdagiv), which are infested with a red greenhouse spider mite of all stages (Teigapuspyv5 igiisaye), are sprayed with a preparation of an active compound of the desired concentration.

After 6 days, determine the effectiveness expressed in 95. 100 96 means that all individuals of the spider mite have died; 0 95 means that none of the individuals of the spider mite died.

In this test, for example, the following combination of production examples shows an efficiency of 90 95 at an application rate of 500 g/ha: 10

In this test, for example, the following compounds of the production examples show an efficiency of 100 95 at an application rate of 500 g/ha: 1,2,3,4,5,6, 7, 8, 9.

The Sieposerpaides gaeii5 Oral Invasion Test (STESEE)

Solvent: 1 mass part of dimethyl sulfoxide

In order to obtain a suitable preparation of the active compound, 10 mg of the active compound is mixed with 0.5 ml of dimethyl sulfoxide. Part of the concentrate is diluted with citrated blood of cattle, and the desired concentration is obtained.

Approximately 20 hungry adult fleas (Steposerpaiide5 Theii5) are placed in a chamber, which is closed from above and below with a gauze cloth. A metal cylinder, the lower end of which is covered with parafilm, is placed in the chamber. The cylinder contains blood/active compound preparation that can be absorbed by fleas through the parafilm membrane. After 2 days, dead pests are determined in uv. 100 95 means that all fleas have died; 0 95 means that none of the fleas died.

З In this test, for example, the following combination of production examples shows that at the application rate of 100 parts per million action 80 9: 7.

In this test, for example, the following compounds of the production examples show, at a rate of application of 100 ppm. action 100 9: 2, 6, 8, 9, 10.

Tests for Isis sirhip (OSISO)

Solvent: dimethyl sulfoxide

To obtain a suitable preparation of the active compound, 10 mg of the active compound is mixed with 0.5 ml of dimethyl sulfoxide, and the concentrate is diluted with water to the desired concentration.

Containers containing horse meat, treated with the preparation of the active compound of the desired concentration, are populated with approximately 20 larvae of Hisiia syrgipa.

After 2 days, dead pests are determined in o. 100,906 means that all larvae have died; 0 95 means that there are no dead larvae.

In this test, for example, the following compounds of the preparation examples show an efficiency of 100 95 at an application rate of 100 parts per million: 6, 7, 8, 9, 10.

Tests on Mizz dotewiis (MOZSOO)

Solvent: dimethyl sulfoxide

To obtain a suitable preparation of the active compound, 10 mg of the active compound is mixed with 0.5 ml of dimethyl sulfoxide, and the concentrate is diluted with water to the desired concentration.

Containers containing a sponge treated with a preparation of an active compound of the desired concentration are populated by adults of Myz5sa doteviisa.

After 2 days, dead pests are determined in bo. 100 9o means that all the flies died; 0 Pho means that none of the flies died.

In this test, for example, the following compounds of the preparation examples show an efficiency of 100 95 at an application rate of 100 parts per million: 6, 7, 8, 10.

Tests for VoorpiYiv5 tisgoria5 (VOORMI, injection)

Solvent: dimethyl sulfoxide

To obtain a suitable preparation of the active compound, 10 mg of the active compound is mixed with 0.5 ml of the solvent, and the concentrate is diluted with the solvent to the desired concentration. A solution of the active compound is injected into the abdominal cavity (Voorpyi5 tisgorii5), and the animals are transferred to cups and kept in a room with a controlled atmosphere. Activity is assessed by laying 60 fertilized eggs.

After 7 days, determine the efficiency expressed in Fo. 100 90 means that none of the ticks laid any number of fertilized eggs.

In this test, for example, the following compounds of the preparation examples show an efficiency of 100 95 at the application rate of 20 μg / animal: 2, 6, 7, 8, 9, 10.

Tests for VoorpyYy5 tisgoriz (OR)

Experimental animals: adult, bled VoorpyYy5 tisgorii5 female individuals of the ZR-resistant strain RagKkPygvi.

Solvent: dimethylsulfoxide mg of the active compound is dissolved in 0.5 ml of dimethylsulfoxide. In order to obtain a suitable preparation, the solution of the active compound is diluted with water to the concentration desired in each case.

This preparation of the active compound is pipetted into test tubes. 8-10 ticks are transferred to an additional test tube with holes. The test tube is immersed in the composition of the active compound, and all ticks are completely wet. After the liquid drains, the ticks are transferred to the filter disk in plastic cups and kept in an artificial climate chamber. Activity is assessed after 7 days by laying fertilized eggs. Eggs, the fertility of which is not visible from the outside, are stored in glass tubes in a cabinet with a controlled atmosphere until the larvae hatch. An efficiency of 100 95 means that none of the ticks laid any number of fertilized eggs.

In this test, for example, the following compounds of the preparation examples show an efficiency of 100 95 at an application rate of 100 parts per million: 6, 8, 9, 10.

Tests for Atbvriuotta peragagit (AMVUNE)

Solvent: dimethyl sulfoxide

To obtain a suitable preparation of the active compound, 10 mg of the active compound is mixed with 0.5 ml of dimethyl sulfoxide, and the concentrate is diluted with water to the desired concentration.

Tick nymphs (Atriuotta pergaeitis) are placed in perforated plastic cups and immersed in the desired concentration of the compound for one minute. Ticks are transferred to filter paper in a petri dish and stored in a controlled atmosphere cabinet.

After 42 days, dead pests are determined in bo. 100 9o means that all ticks have died; 0 Uo means that none of the ticks died.

З In this test, for example, the following combination of production examples shows that at the application rate of 100 parts per million action 100 95:10

B. Comparative biological tests

Tests on 5roadoriega ytidiregda (ZROOEEK, spray treatment)

Solvents: 78.0 mass parts of acetone and 1.5 mass parts of dimethylformamide

Emulsifier: 0.5 mass parts of alkylaryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 mass part of the active compound is mixed with the prescribed amounts of solvents and emulsifier, and the concentrate is diluted with water containing the emulsifier to the desired concentration (in g/ha).

Plates of corn leaves (7ea taub5) are sprayed with the composition of the active compound of the desired concentration and, after drying, are inhabited by caterpillars of the scoop (Zrodoriega Igidiregaa).

After the end of the desired period of time, determine the action in bo. 100 95 means that all caterpillars have died; 0 96 means that none of the caterpillars died.

In this test, for example, the following compounds of the preparation examples show a higher efficiency compared to the known state of the art: see table

Tests on Mulyz5 (MU2ORE, spray treatment)

Solvents: 78.0 mass parts of acetone and 1.5 mass parts of dimethylformamide

Emulsifier: 0.5 mass parts of alkylaryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 mass part of the active compound is mixed with the prescribed amounts of solvents and emulsifier, and the concentrate is diluted with water containing the emulsifier to the desired concentration (in g/ha).

Plates of Beijing cabbage leaves (Vgazzisa recKipepz5ib5), infested with peach green aphid (Muy5 regsisae) of all stages, are sprayed with the preparation of the active compound of the desired concentration.

After the end of the desired period of time, determine the action in bo. 100 95 means that all aphids died; O 95 means that none of the aphids died.

In this test, for example, the following compounds of the preparation examples show a higher efficiency compared to the known state of the art: see table

Tests on Rpaedop (RNAESO, spray treatment)

Solvents: 78.0 mass parts of acetone 1.5 mass parts of dimethylformamide bo Emulsifier: 0.5 mass parts of alkylaryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 mass part of the active compound is mixed with the prescribed amounts of solvents and emulsifier, and the concentrate is diluted with water containing the emulsifier to the desired concentration (in g/ha).

Plates of Beijing cabbage leaves (Vgazvisa reKipep5iz5) are sprayed with the preparation of the active compound of the desired concentration and, after drying, are inhabited by the larvae of the horseradish leaf-eater (Rpaedop sospiveagiaye).

After the end of the desired period of time, determine the action in bo. 100 95 means that all beetle larvae have died; 0 9o means that none of the beetle larvae died.

In this test, for example, the following compounds of the preparation examples show a higher efficiency compared to the known state of the art: see table

Tests on Teigapuspa5, OR-resistant (TETKIRE, spray treatment)

Solvents: 78.0 mass parts of acetone and 1.5 mass parts of dimethylformamide

Emulsifier: 0.5 mass parts of alkylaryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 mass part of the active compound is mixed with the prescribed amounts of solvents and emulsifier, and the concentrate is diluted with water containing the emulsifier to the desired concentration (in g/ha).

Plates of bean leaves (RPazeoish5 miiYidagib), which are infested with the red greenhouse spider mite of all stages (Teigapuspyv5 igiisaye), are sprayed with the preparation of the active compound of the desired concentration.

After the end of the desired period of time, determine the action in bo. 100 95 means that all individuals of the spider mite have died; 0 95 means that none of the individuals of the spider mite died.

In this test, for example, the following compounds of the preparation examples show a higher efficiency compared to the known state of the art: see table

Tests on Riadop sospieagiae, spray treatment (RNAESO)

Solvent: 7 mass parts of dimethylformamide

Emulsifier: 2 mass parts of alkylaryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 mass part of the active compound is mixed with the prescribed amounts of solvent and emulsifier, and the concentrate is diluted with water containing the emulsifier to the desired concentration (ppm). If you need to add

From ammonium salts and/or penetrants, in each case they are added to the drug solution at a concentration of 1000 ppm.

Cabbage leaves (Vgazzisa oIegasea) are sprayed with the preparation of the active compound of the desired concentration, and are inhabited by the larvae of the horseradish leaf-eater (Rpaedop sospieagiae).

After the desired period of time, dead pests are determined at 95. 100 95 means that all beetle larvae have died; 0 9o means that none of the beetle larvae died.

In this test, for example, the following combination of preparation examples shows a higher efficiency compared to the known prior art: see table

Tests for Rishiella huioziveia, spray treatment (P ШТМА)

Solvent: 7 mass parts of dimethylformamide

Emulsifier: 2 mass parts of alkylaryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 mass part of the active compound is mixed with the prescribed amounts of solvent and emulsifier, and the concentrate is diluted with water containing the emulsifier to the desired concentration (ppm). If it is necessary to add ammonium salts and/or penetrants, in each case they are added to the drug solution at a concentration of 1000 ppm.

Cabbage leaves (Vgazzisa oIegasea) are sprayed with the preparation of the active compound of the desired concentration and infected with the larvae of the cabbage moth (RisheiPa huiozieteiPa).

After the desired period of time, dead pests are determined at 95. 100 95 means that all caterpillars have died; 0 9o means that none of the caterpillars died.

In this test, for example, the following combination of preparation examples shows a higher efficiency compared to the known prior art: see table

Tests on 5roadorieg Ihydiregaa, spray treatment (ZROYUEK)

Solvent: 7 mass parts of dimethylformamide

Emulsifier: 2 mass parts of alkylaryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 mass part of the active compound is mixed with the prescribed amounts of solvent and emulsifier, and the concentrate is diluted with water containing the emulsifier to the desired concentration (ppm). If it is necessary to add ammonium salts and/or penetrants, in each case they are added to the drug solution at a concentration of 1000 ppm. 60 Cotton leaves (Soz5zurisht Pig5shiit) are sprayed with the composition of the active compound of the desired concentration, and are inhabited by caterpillars of the scoop (Zroadoriega Ihydiregaa).

After the desired period of time, dead pests are determined at 95. 100 95 means that all caterpillars have died; 0 9o means that none of the caterpillars died.

In this test, for example, the following compounds of the preparation examples show a higher efficiency compared to the known state of the art: see table

Apidega Neiyot Test, Spray Treatment (NEGIAC)

Solvent: 7 mass parts of dimethylformamide

Emulsifier: 2 mass parts of alkylaryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 mass part of the active compound is mixed with the prescribed amounts of solvent and emulsifier, and the concentrate is diluted with water containing the emulsifier to the desired concentration (ppm). If it is necessary to add ammonium salts and/or penetrants, in each case they are added to the drug solution at a concentration of 1000 ppm.

Cotton plants (Со55уришт Вигешит) are sprayed with the composition of the active compound of the desired concentration and, after drying, they are inhabited by caterpillars of the cotton bollworm (Neioiipi5 agptidega).

After the desired period of time, dead pests are determined at 95. 100 95 means that all caterpillars have died; 0 9o means that none of the caterpillars died.

In this test, for example, the following combination of preparation examples shows a higher efficiency compared to the known prior art: see table

Tests on Teigapuspiz igiisaee, spray treatment, OR-resistant (TETKETSOR)

Solvent: 7 mass parts of dimethylformamide

Emulsifier: 2 mass parts of alkylaryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 mass part of the active compound is mixed with the prescribed amounts of solvent and emulsifier, and the concentrate is diluted with water containing the emulsifier to the desired concentration (ppm). If it is necessary to add ammonium salts and/or penetrants, in each case they are added to the drug solution at a concentration of 1000 ppm.

Bean plants (Rpazeoiiz5 miiYidagiv5), which are heavily infested with the red greenhouse spider mite of all stages (Teigapuspy5 igpisaye), are sprayed with a preparation of the active compound of the desired

From concentration.

After the desired period of time, determine the action in bo. 100 95 means that all individuals of the spider mite have died; 0 95 means that none of the individuals of the spider mite died.

In this test, for example, the following compounds of the preparation examples show a higher efficiency compared to the known state of the art: see table

Miiaragmaya Ishdep5 trials, spray treatment (MIGAGO)

Solvents: 52.5 mass parts of acetone, 7 mass parts of dimethylformamide

Emulsifier: 0.5 mass parts of alkylaryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 mass part of the active compound is mixed with the prescribed amounts of solvents and emulsifier, and the concentrate is diluted with water containing the emulsifier to the desired concentration. If it is necessary to add ammonium salts and/or penetrants, in each case they are added to the drug solution at a concentration of 1000 ppm.

Rice plants (Ogula zaina) are sprayed with the preparation of the active compound of the desired concentration, and then infested with larvae of the brown delphacid (Miiaragmaia Isdepv).

After the end of the desired period of time, determine the action in bo. 100 95 means that all delfacid individuals have died; 0 95 means that none of the delfacid individuals died.

In this test, for example, the following compounds of the preparation examples show a higher efficiency compared to the known state of the art: see table

Tests on Egapkipivia ossidepiaii5, spray treatment (EKAMOS)

Solvents: 52.5 mass parts of acetone, 7 mass parts of dimethylformamide

Emulsifier: 0.5 mass parts of alkylaryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 mass part of the active compound is mixed with the prescribed amounts of solvents and emulsifier, and the concentrate is diluted with water containing the emulsifier to the desired concentration. If it is necessary to add ammonium salts and/or penetrants, in each case they are added to the drug solution at a concentration of 1000 ppm.

Leaf plates of common bean (RpazeoYi5 miYidagibe) are sprayed with the preparation of the active compound of the desired concentration, and then infected with a mixed population of thrips (Rhapkiipiv|ia ossidepiai! iv). bo After the desired period of time, determine the action in bo. 100 95 means that all thrips have died; 0 95 means that none of the thrips individuals died.

In this test, for example, the following compounds of the preparation examples show a higher efficiency compared to the known state of the art: see table

Tests on 1 ihiotu?a ihigoii, spray treatment (HIKITK)

Solvents: 52.5 mass parts of acetone, 7 mass parts of dimethylformamide

Emulsifier: 0.5 mass parts of alkylaryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 mass part of the active compound is mixed with the prescribed amounts of solvents and emulsifier, and the concentrate is diluted with water containing the emulsifier to the desired concentration. If it is necessary to add ammonium salts and/or penetrants, in each case they are added to the drug solution at a concentration of 1000 ppm.

Plates of bean leaves (Rpazeoii5 miiYidagi5), which are infested with the larvae of the transient fly (Shpoptua igitoii), are sprayed with the preparation of the active compound of the desired concentration.

After the end of the desired period of time, determine the action in bo. 100 95 means that all passing flies have died; 0 95 means that none of the mowing flies died.

In this test, for example, the following compounds of the preparation examples show a higher efficiency compared to the known state of the art: see table

The Oral Invasion of Sipocerpaiella Tei5 Test (STESEE)

Solvent: 1 mass part of dimethyl sulfoxide

In order to obtain a suitable preparation of the active compound, 10 mg of the active compound is mixed with 0.5 ml of dimethyl sulfoxide. Part of the concentrate is diluted with citrated blood of cattle, and the desired concentration is obtained.

Approximately 20 hungry adult fleas (Sieposerpaiide5 teje) are placed in a chamber, which is closed from above and below with a gauze cloth. A metal cylinder, the lower end of which is covered with parafilm, is placed in the chamber. The cylinder contains blood/active compound preparation that can be absorbed by fleas through the parafilm membrane.

After the desired period of time, dead pests are determined at 95. 100 95 means that all fleas have died; 0 95 means that none of the fleas died.

zo In this test, for example, the following compounds of the preparation examples show a higher efficiency compared to the known prior art: see table

Tests on Mizz dotewiis (MOZSOO)

Solvent: dimethyl sulfoxide

To obtain a suitable preparation of the active compound, 10 mg of the active compound is mixed with 0.5 ml of dimethyl sulfoxide, and the concentrate is diluted with water to the desired concentration.

Containers containing a sponge treated with the composition of the active compound of the desired concentration are populated by adults of Myz5sa doteviisa.

After the desired period of time, dead pests are determined at 95. 100 95 means that all flies have died; 0 95 means that none of the flies died.

In this test, for example, the following compounds of the preparation examples show a higher efficiency compared to the known state of the art: see table

Voorpiya5 teshoria5 test (OIR)

Experimental animals: adult infused with blood Voorpii5 ptisgoriai5 female individuals of the 5P-resistant strain RagkVPigvi

Solvent: dimethyl sulfoxide 10 mg of the active compound is dissolved in 0.5 ml of dimethyl sulfoxide. In order to obtain a suitable preparation, the solution of the active compound is diluted with water to the concentration desired in each case (ppm).

This preparation of the active compound is pipetted into test tubes. 8-10 ticks are transferred to an additional test tube with holes. The test tube is immersed in the composition of the active compound, and all ticks are completely wet. After the liquid drains, the mites are transferred to the filter disc in plastic cups and kept in a room with a controlled atmosphere.

Activity is assessed after the desired time has passed by the laying of fertilized eggs.

Eggs, the fertility of which is not visible from the outside, are stored in glass tubes in a cabinet with a controlled atmosphere until the larvae hatch. Action 100 95 means that none of the ticks laid any number of fertilized eggs.

In this test, for example, the following compounds of the preparation examples show a higher efficiency compared to the known state of the art: see table

Tests for VoorpPyi5 tpisgoria5 (VOORMI, injection) 60 Solvent: dimethylsulfoxide

To obtain a suitable preparation of the active compound, 10 mg of the active compound is mixed with 0.5 ml of the solvent, and the concentrate is diluted with the solvent to the desired concentration (in μg/animal).

A solution of the active compound is injected into the abdominal cavity (Voorpyii5 ptisgorii5), and the animals are transferred into cups and kept in a room with a controlled atmosphere.

After 7 days, the efficiency expressed in 95 is determined. The activity is evaluated by the laying of fertilized eggs. 10095 means that none of the ticks laid any number of fertilized eggs.

In this test, for example, the following compounds of the preparation examples show a higher efficiency compared to the known state of the art: see table

View - |to Activity

B EE MU2ORE 20 g/ha O bdpo

E shchi TETVOV 20 g/ha O b dpo

Application Me Ik MU Fr

In 9 1K- sh RNAESO| 0.8 parts per million 0 7 dpo known from MO sn, from MPA | 20 g/ha 0 7 dpo 2010/051926 n, 7 STESEEI Och/mln. | 30 2dpo

Ag no 0.032 ich VOORMI μg/animal O 7 dpo ch./million. 0 7 dpo

E MU2ORE 20 g/ha 70 bdpo

M GE EE TETVOV 20 g/ha 100 6 dpo

Application Me 6 E E RNAESO)| 0.8 parts per million 100 7 dpo in accordance with U about MPA 20 g/ha 90. 7 dpo - (c) invention SHI and STESEE SHY 80 2 dpo that their VOORMI 70. 7 dpo sn, these mcg/animal 20 h./million. 100 7 dpo more MU2ORE 100 g/ha O /bdpo of, DY RNAESO| 0.8 h/mln. 5 7dpo

Application Me IC- E Y sn, RIOTMA) 20 h./mln. B T7dpo 132 MM ZROOEV| 20 hours/million | 50 7 dpo is known from UMO IJ in, si TETVIOVI| 4 h/mln. 30 7 dpo 2010/051926 and about STESRE| 0Vh/mln. 30 2 dpo

Ag No 0.032

M VOORMI eye-catching | 0/7 dpo 20 hours/million. З0 7 dpo

MU2ORE 100 g/ha 100 6 dpo vv AK RNAESO | 0.8 parts per million 100 7 dpo

E E M RIG OTMA 20 hours/million. 100 7 dpo

Application Me 8 KM oi ЗРООЕВ| 20 hours/million | 100 7 dpo in accordance with M TETVOV 4 hours/million. 95 7 according to the invention | M M STESSRE | 0.8 h/mln. 90 2 dpo l si VOORMI 0/0032 100. 7 dpo mcg/animal 20 parts/million. 100 7 dpo in E ZROOEN 20 h./mln. 20 7 dpo

Application Mo IR-1 i m NEPAV 20 ch./million. 45 7 dpo known from UMO E M 2010/051926 from Zka Me snu TETVOV 4 hours/million. 40 7 dpo

Ag 07 mn EVAMOS 20 g/ha OO 7 dpo

I tsn MISASO 500 g/ha OO 7 dpo -kY " a o U

-

Structure Concentration

E in-4 /x MU7ORE 100 g/ha O Edpo

Enm, o

Application Mo IC- s EVAMOS 500 g/ha bO 7 dpo 296 known from UMO nm" en, vita 500 g/ha O 7 dpo 2010/051926 and d2 o | /m

E T/,

JSC MISASO 500 g/ha 0/7 dpo

E E

I

MU2ORE 5OO g/ha O bdpo

RNAESO 20 g/ha 0 7 dpo

RI Shtma 20 h./mln. 0 7 dpo

Application Me IR- nm. ro ZROOREV 20 h./mln. At 7 dpo 47 si NEPAN 20 hours/million. At 7 p.m., 20 hours/million is known from the TETAVOV MO. ZO 7 dpo 2010/051926 nok EVAMOS 500 g/ha O 7 dpo dg about MSA 500 g/ha 0/7 dpo there are STESEEE! h/m | 50 2dpo

Y E MiY5SrO| 100 parts per million 0 2dpo

IS

What; VOORMI 0.8 μg/animal 50 7 dpo

I" MU7ORE 20 g/ha 0 bdpo

Application Me Ik- NM. 2»O RNAESO 100 g/ha 0 7 dpo 286 s known from UMO STESEE 4 hours/million. 0 2 dpo 2010/051926 no ey, le r VOORMI| 100 hours/ml. ) 40 7 dpo

IS

So 0.16

E E . of mcg/animal 20 7 dpo

Application Me Ik- BE o s MU7ORE 20 g/ha O |v dpo 279 is XX sno |RNABESO) 20 g/ha o |7 dpo known from MO E and: Z

ОО 0/5 926 ; What M I k ZROOEV 100 g/ha BO |7 dpo

Ag b SN» TETVOV) 4 ch/mln. 0 |7 dpo

Application Me IC- in, with RI Shtma 20 h./mln. 65 |7 dpo 280 E o RNAESO 4 hours/million. 0 |7 dpo is known from MO E with M so |9РООЕВ| h/m | 40 | 7 dpo 2010/051926 E Hm, I M NESHPAV | 100 parts per million 0 |7 dpo to shi: Sn MAG 100 g/ha O | 7 dpo

-

MU2ORE 500 g/ha 100 | b dpo 100 g/ha 100 | b dpo g/ha 80 |6 dpo

RNAESO 100 g/ha 100 | 7 dpo 20 g/ha 100 | 7 dpo 4 hours/million. 100 | 7 dpo

ZROOEN 100 g/ha 100 | 7 dpo 20 hours/million. 100 | 7 dpo

RI Shtma 20 h./mln. 100 | 7 dpo

E E xx NEPAN 100 h./mln. 100 | 7 dpo

ME te r and 20 h/mln. | 100 ) 7 dpo

TETVOV 20 h./mln. 100 | 7 dpo

Application Me 10 E and nm a4h/million. | 1007 according to the invention. to LE n EVAMOS| 500 g/a 100 |7 dpo

M He) 20 g/ha 90 /|7 dpo her in, VITA 500 g/ha 100 | 7 dpo

SN, SI MIG AGY 500 g/ha 100 | 7 dpo 100 g/ha 100 | 7 dpo

STACEE 20 h/mln. 100 |2 dpo 4 hours/million. 98 |2 dpo 0.8 hours/million. 90 |2 dpo

MIOBSrO| 100 parts per million 100 |2 dpo

VOORMI /|0.8 μg/animal!| 100 | 7 dpo 0.16 μg/animal 80 | 7 dpo 100 h./mln. 100 | 7 dpo street MU2IRE 100 g/ha 0 bdpo

Application Me IC- and Otse A 175 and NM RNAESO)| "4 hours/million 10 7 dpo known from MO / Kh N 2010/051926 M. M o d2 y Se MISASO 500 g/ha 0 7 dpo sn. 9 Ve kish; MUCHORE| cho0gla 0100 vdpo

IS

Application Me 14 vii 90,000" GNABSOY odchumlyu. | 100 7 dpo in accordance with She XX of the invention of Her nm OO

SN" and MPA 500 g/ha 80 4dpo

IJ

E E

Application Mo IC- E EE KE MU2ORE 100 g/ha O bdpo 155 E E also: known from MO LE CH to 91926 and se TETVOV| 100 g/ha 0 bdpo sn. about E

Substance Structure Type Concentration З5 Activity of the structure of the animal centrats dpo

E E

E E E E there is

MU2IORE 100 g/ha 100 6 dpo and E

Gu

Application Mo 14 la according to sleep MM invention E o TETAOV 100 g/ha 100 6 dpo

NM fairy

Claims (12)

FORMULA OF THE INVENTION 1. The compound of the general formula (I) and 72 li 1 M Kk o M 5 D and AT SA, Az M rashch ve (v! ; (I) in which B' means hydrogen, Ci-Cv-alkyl, Co-Cv- alkenyl, C2-C6-alkynyl, C1-C6-alkylcarbonyl, C1-C6- alkoxycarbonyl, cyano-C1-C6-alkyl, aryl-(C1-C3)-alkyl or heteroaryl-(C1-C3)-alkyl; chemical group A; means CB, A means SEZ, Az means SEU, Ag means CE; Bg, VUZ, B and E? independently of each other mean hydrogen, halogen or Ci-Cv-alkyl; UM means oxygen; Vb means hydrogen, Ci- C 1 -alkyl, aryl-(C 1 -C 3 )-alkyl, C 1 -C 6 -alkylcarbonyl or C 1 -C 1 -C 6 - alkoxycarbonyl; o means E " | : E means bond; B" means cyano; 42 means optionally substituted C .1-Cv-haloalkyl or C3-Cv-halocycloalkyl, 22 means halogen, Ci-Cv-haloalkyl, Ci-Cv-alkylthio, Ci-Cv-alkylsulfinyl or C:1-Cv-alkylsulfonyl, and 73 means hydrogen or C: -Cv-alkyl, Ci-C4-alkenyl, Ci-Ca-alkynyl or Ci-Cv-haloalkyl. 2. The compound of the general formula (I) according to item 1, in which B' means hydrogen, methyl, ethyl, methylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, t-butylcarbonyl, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, cyanomethyl, benzyl, pyrid-2-ylmethyl , pyrid-3-ylmethyl or pyrid-4-ylmethyl; chemical group A; means SKZ, A means SEZ, Az means SEU, Ag means SE; B2 and E5 mean hydrogen; BZ and 27 are independently hydrogen, fluorine, chlorine, bromine or methyl; UM means oxygen; WU means hydrogen, methyl, ethyl, methylcarbonyl, n-propylcarbonyl, methoxycarbonyl or ethoxycarbonyl; o means E pi E means connection; B" means cyano; 7! means trifluoromethyl, pentafluoroethyl, 1-chlorocyclopropyl or 1-fluorocyclopropyl, 72 means halogen, trifluoromethyl, methylthio, methylsulfinyl or methylsulfonyl, and 73 means methyl, ethyl, n-propyl, 2-propenyl, 1-propynyl or 2,2,2-trifluoroethyl. 3. The compound of the general formula (I) according to item 1 or 2, in which 7" means trifluoromethyl, 1-chlorocyclopropyl, 1-fluorocyclopropyl or pentafluoroethyl, 727 means trifluoromethyl, methylthio, methylsulfinyl, methylsulfonyl, chlorine or bromine, 73 means methyl, ethyl or n-propyl; B' means hydrogen, methyl, ethyl, methylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, t-butylcarbonyl, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, cyanomethyl, benzyl, pyrid-2-ylmethyl, pyrid-3-ylmethyl or pyrid- 4-ylmethyl; A", dg and A? mean SN, Az means IED; IN? means fluorine, chlorine, bromine or iodine; A means hydrogen, methyl or ethyl; MM stands for oxygen; and Zo o means 1-cyanocyclopropyl. 4. The compound of the general formula (I) according to any of items 1-3, in which 7 means trifluoromethyl, 1-chlorocyclopropyl, 1-fluorocyclopropyl or pentafluoroethyl, 77 means trifluoromethyl or chlorine, 73 means methyl, A" means hydrogen, methyl , ethyl; At, Ag and A" mean CH; Az means SVU; B" means chlorine; A means hydrogen, methyl or ethyl; M stands for oxygen and o stands for 1-cyanocyclopropyl. 5. Application of compounds of the general formula (I) according to any of items 1-4 for the control of insects, arachnids and nematodes. 6. The compound according to any of items 1-4 for use as a medicinal product. 7. Application of compounds of the general formula (I) according to any of items 1-4 and b for obtaining pharmaceutical compositions for combating parasites on animals. 8. The method of obtaining compositions for the protection of agricultural crops, which include compounds of the general formula (I) according to any of items 1-4 and conventional fillers and/or surface-active substances. FOR 9. The method of pest control, which is characterized by ensuring the effect of the compound of the general formula (I) according to any of items 1-4 on pests and/or their place of distribution. 10. The use of compounds of the general formula (I) according to any of items 1-4 for the protection of plant propagation material, in particular seeds. 11. A compound of the general formula (IMa) or (IMB) MO, Mn, v2 v v2 v M M nn y nn y M M k Kk 4 4 o ; (Mb) about ; (Ma) where B2, VU, Be and Ex independently of each other mean hydrogen, halogen, cyano, nitro, optionally substituted C.i.-Cv-alkyl, Ci-Cv-haloalkyl, C3-Cv-cycloalkyl, C3- C1-Cv-halocycloalkyl, C1-Cv-Alkoxy, C-Cv-Haloalkyloxy, C-Cv-Alkylthio, C-Cv-haloalkylthio, C-Cv-alkylsulfinyl, C1-Cv-haloalkylsulfinyl, C-Cv-Alkylsulfonyl, C-Cv- haloalkylsulfonyl, C-Cv-alkylamino, M,M-di-C1-Cv-alkylamino, M-C1-Cv-alkylaminocarbonyl, M-C3-Cv-cycloalkylaminocarbonyl, or (C1-C3-alkyloxy)carbonyl. 12. A compound of the general formula (Ma) or (Mb) х х 7 и хх о-. /х o-. in n M M. M M o | o uk Z (Mb) 7 (Ma) de X! means halogen, cyano and C1-C-haloalkyl, 72 means halogen, cyano, nitro or optionally substituted C1-C8-haloalkyl, C1-C8-alkylthio, C1-C8-haloalkylthio, C1-C8-alkylsulfinyl, Ci-Cv-haloalkylsulfinyl, Ci-Cv-alkylsulfonyl, C1-Cv-haloalkylsulfonyl, 73 means hydrogen or optionally substituted Ci-Cv-alkyl, Ci-C4-alkenyl, Ci-C4-alkynyl, C1-Cv-haloalkyl , and Y means optionally substituted C.:-Cv-alkyl.